1 Introduction
Transition metal-catalyzed asymmetric allylic alkylation (AAA) has emerged as a versatile and efficient method for the enantioselective construction of allylic stereocenters, which are pivotal motifs in bioactive molecules and chiral synthons.[1] The past two decades have seen transformative advances in transition metal-catalyzed asymmetric allylic alkylation, where palladium, rhodium and iridium have emerged as the dominant catalytic platforms, enabling precise stereocontrol in the construction of challenging allylic stereocenters.[2] In these transformations, the choice of ally-lic electrophiles is critical for achieving optimal reactivity and selectivity. Early studies on rhodium-and iridium-catalyzed systems predominantly employed linear allylic esters as substrates. However, recent efforts have shifted toward the use of more sustainable branched allylic alcohols, offering both environmental and synthetic advan-tages.[3] Notably, allenes have been successfully employed as versatile substrates in asymmetric allylic alkylation reactions (Scheme 1a).[4] Recent breakthroughs include Carreiraʼs work in 2018,[5] where they developed an Ir-cata-lyzed allylation of branched allylic carbonates using trimethyl orthoacetate as an enolate surrogate. Around the same time, the Youʼs group[6] reported an asymmetric Rh-catalyzed allylic alkylation of branched alcohols with 1,3-diketones, employing readily available allylic alcohols as starting materials while achieving high regio-and enantio-selectivity for both aryl and aliphatic allylic alcohols. More recently, Yang and coworkers demonstrated an iridium-catalyzed allylic alkylation of racemic branched alkyl-substituted allylic acetates or alcohols with malonates (Scheme 1a).[7]
The development of sustainable and atom-economical methodologies for C—C bond formation is a significant challenge in synthetic chemistry. The ability to convert inert C—H bonds into C—C bonds has driven the development of various atom-and step-efficient strategies.[8] Among these, transition metal-catalyzed allylic C—H bond functionalization has emerged as a particularly promising approach for accessing complex molecular structures and enabling efficient late-stage functionalization.[9] Recently, Jeganmohan and coworkers reported a Rh(III)-catalyzed allylic C—H alkylation of unactivated alkenes using diazo compounds, proceeding via a migratory insertion mechanism (Scheme 1b).[10] Notably, this approach selectively suppresses competing pathways such as cyclopropanation, allylic olefination, and carbene dimerization, thereby enabling efficient and direct C—C bond formation at the allylic position. While remarkable progress has been achieved in transition metal-catalyzed asymmetric allylic functionalization, the direct enantioselective allylic C—H alkylation of unactivated alkenes remains an unsolved challenge. The formidable obstacles stem from two fundamental limitations: (i) the pronounced thermodynamic stability of allylic C—H bonds in simple alkenes, and (ii) the intricate stereoelectronic requirements for simultaneous regio-and enantiocontrol in C—H activation processes. Inspired by Jeganmohan's study, we propose that chiral cyclopentadienyl rhodium(III) CpxRhIII catalysts would provide an efficient and selective approach for achieving asymmetric allylic C—H alkylation of unactivated alkenes. This approach harnesses three key design elements: (1) the inherent electrophilicity of RhIII centers for efficient C—H bond cleavage, (2) the rigid, well-defined chiral environment of the Cpx ligand provides optimal steric control for enantio-selectivity; and (3) the tunable nature of the catalyst system allows for the regulation of regiochemical outcomes (Scheme 1c).
2 Results and discussion
Our investigation began with the enantioselective C—H allylation of unactivated 1-octene (1a) using dibenzyl 2-diazomalonate (2a) under Rh(III) catalysis.[11] Initial conditions employing chiral CpxRh(III) complex Rh-1 with AgSbF6/Cu(OAc)2 additives in 2,2,2-trifluoroethanol (TFE) at 25 ℃ under N2 afforded the branched product 3a with modest efficiency (42% yield, 56% ee, B/L (branched/ linear)=1.5∶1; Table 1, Entry 1). Screening of BINOL-derived CpxRh(III) catalysts (Rh-2 to Rh-5) proved unsatisfactory, yielding 3a with poor to moderate results (20%~35% yield, 15%~51% ee, B∶L=1.2∶1~2.3∶1; Entries 2~5). Solvent evaluation revealed that TFE was the optimal solvent (Entries 6~8). Control experiments established the essential role of AgSbF6, as no reaction occurred in its absence (Entry 9). Optimal performance was achieved with 2.0 equiv. of AgSbF6, providing 3a with good yield, high enantioselectivity and B/L ratio (Entry 11, 71% yield, 87% ee, B∶L=3.1∶1). AgSbF6 served as a critical additive for the generation of the active cationic Rh(III) catalyst, thereby increasing the system's reactivity and chiral induction. Notably, alternative silver or copper additives consistently diminished both yield and enantioselectivity.
Table 1 Reaction optimization of asymmetric alkylationa
|
| Entry | Rh | Solvent | AgSbF6 (equiv.) | Yield/% | ee/% | B/L |
|---|---|---|---|---|---|---|
| 1 | Rh-1 | TFE | 0.1 | 42 | 56 | 1.5∶1 |
| 2 | Rh-2 | TFE | 0.1 | 25 | 15 | 1.1∶1 |
| 3 | Rh-3 | TFE | 0.1 | 20 | 35 | 1.3∶1 |
| 4 | Rh-4 | TFE | 0.1 | 35 | 49 | 2.4∶1 |
| 5 | Rh-5 | TFE | 0.1 | 32 | 51 | 2.1∶1 |
| 6 | Rh-1 | HFIP | 0.1 | 43 | 40 | 2.8∶1 |
| 7 | Rh-1 | DCE | 0.1 | 48 | 37 | 2.2∶1 |
| 8 | Rh-1 | MeOH | 0.1 | 48 | 54 | 1.2∶1 |
| 9 | Rh-1 | TFE | — | NR | — | — |
| 10 | Rh-1 | TFE | 1.0 | 60 | 70 | 3.2∶1 |
| 11 | Rh-1 | TFE | 2.0 | 71 | 87 | 3.3∶1 |
| 12 | Rh-1 | TFE | 2.5 | 68 | 87 | 3.2∶1 |
a Reaction conditions: 1a (0.3 mmol), 2a (0.1 mmol), Rh cat (2.5 mol%), AgSbF6 (x eqiuv.), Cu(OAc)2 (2.0 equiv.), solvent (0.2 mol/L), r.t., 18 h. Isolated yields (branched and linear). Determined by HPLC analysis on a chiral stationary phase. The radiometric ratio (branched/linear) was obtained by analysis of the 1H NMR spectra of the crude reaction mixtures. |
With optimized conditions established, the substrate scope using various unactivated aliphatic alkenes was explored. As shown in Table 2, the reaction delivered products 3b~3f in 45%~77% yields, 85%~92% ee, and 1.1∶1~4.8∶1 B/L ratios. Allylbenzene-type substrates afforded product 3g in good yield and ee, but with low B/L selectivity. Other aromatic ring-substituted alkenes also provided the corresponding products 3h~3j in moderate yields, enantioselectivity and B/L ratios. The reaction demonstrated excellent tolerance toward terminal alkenes bearing halogen, hydroxyl and ester groups, yielding the desired products 3k~3q (47%~72% yields, 71%~89% ee, 2∶1~>10∶1 B/L). The heterocyclic ester-substituted alkene was suitable for asymmetric allylic alkylation, yielding product 3r with 38% yield, 75% ee enantioselectivity and 2∶1 B/L ratio. Electron-withdrawing groups (OTs, N-Ts) afforded products 3s~3t in 66%~70% yields with moderate ee and B/L ratios.
Table 2 Substrate scope of unactivated terminal alkenes
|
 |
a Reaction conditions: 1 (0.3 mmol), 2a (0.1 mmol), Rh-1 (2.5 mol%), AgSbF6 (2.0 equiv.), Cu(OAc)2 (2.0 equiv.), TFE (0.2 mol/L), r.t., 18 h. Isolated yields (branched and linear). Enantiomeric excess was determined by HPLC analysis. Regiomeric ratio (branched/linear) was determined by analysis of the 1H NMR spectra of the crude reaction mixtures. b 40 ℃, 48 h. |
Next, we tested diazo compounds with 1-octene 1a. As shown in Table 3, benzyl-and phenyl-substituted diazo compounds reacted smoothly, yielding products 3a and 3u with good yields, enantioselectivity, and B/L ratios. Ethyl-substituted diazo ester derivatives were also compatible, yielding product 3v in 48% yield with 82% ee and 2.5∶1 B/L ratio. Subsequent evaluation of diazo substrates bearing substituted aryl groups revealed that chloro-, bromo-and methyl-substituted derivatives were well tolerated, providing products 3w~3y in moderate to good yields with 60%~73% ee and 2.5∶1~3.3∶1 B/L ratios.
Table 3 Substrate scope of substituted diazo compounds
|
 |
a Reaction conditions: 1a (0.3 mmol), 2 (0.1 mmol), Rh-1 (2.5 mol%), AgSbF6 (2.0 equiv.), Cu(OAc)2 (2.0 equiv.), TFE (0.2 mol/L), r.t., 18 h. Isolated yields (branched and linear). Enantiomeric excess was determined by HPLC analysis. Regiomeric ratio (branched/linear) was determined by analysis of the 1H NMR spectra of the crude reaction mixtures. |
To probe the mechanism, competitive and parallel kinetic isotope effect (KIE) experiments were performed (Schemes 3a, 3b). The observed competitive KIE (kH/kD=6.7) and parallel KIE (kH/kD=2.9) values strongly suggest that allylic C—H bond cleavage represents the rate-determining step in the catalytic cycle.[12]
Based on these results, the mechanism outlined in Scheme 4 was proposed. The active cationic Rh(III) catalyst I forms upon treatment of the chiral CpxRh(III) complex with AgSbF6 in the presence of pivalate. Coordination of alkene 1 to complex I generates intermediate II, which undergoes rate-and enantio-determining allylic C—H activation to form the π-allyl Rh(III) complex III.[13] Subsequent reaction with diazo compound 2 leads to carbene formation, yielding the key Rh(V)-carbene intermediate IV.[10] Reductive elimination from IV affords complex V, which undergoes protonolysis to release product 3 while regenerating the active catalyst.
3 Conclusions
In summary, we report a chiral CpxRh(III)-catalyzed enantioselective allylic C—H alkylation of unactivated alkenes with α-diazocarbonyl compounds. This method features high atom economy, broad substrate scope, and excellent functional group tolerance. Mechanistic investigations, including kinetic isotope effect studies, support a proposed pathway involving allylic C—H activation followed by carbene insertion. This methodology provides a strategic approach to asymmetric allylic C—H functionalization and advances the frontier of C—H activation catalysis. Novel investigations into the asymmetric activation of allylic C—H bonds are currently ongoing in our laboratory.
4 Experimental section
4.1 General information
Commercially available chemicals were obtained from Adamas, Bide Pharmatech Co., Energy Chemical, and TCI and used as received unless otherwise stated. Anhydrous solvent, purchased from Adamas and J&K Scientific, were used as received. All reactions were carried out under the N2 atmosphere in flame-dried glassware. Syringes which were used to transfer anhydrous solvents or reagents were purged with nitrogen prior to use (three times). Thin-layer chroma-tography (TLC) was performed on silica gel Huanghai HSGF254 plates and visualization of the developed chromatogram was performed by fluorescence quenching (λmax=254 nm). Flash chromatography was carried out on SiO2 (silica gel 60, 200~300 mesh). Melting points were corrected and recorded using digital Büchi Melting Point Apparatus B540.
1H NMR and 13C NMR were recorded on a Bruker Avance II-400/500 MHz spectrometer. Solvent used for spectra was chloroform-d. 1H NMR chemical shifts were reported relative to trimethylsilane (TMS) (δ 0.00), chloroform-d (δ 7.26), and 13C NMR are reported relative to chloroform-d (δ 77.16). ESI-HRMS data were acquired using a Thermo LTQ Orbitrap XL Instrument equipped with an ESI source and controlled by Xcalibur software. Enantiomeric excess (ee) value was determined by high-performance liquid chromatography (HPLC) analysis using a chiral stationary phase on Waters B2695 instrument in comparison with the authentic racemates. All the chiral stationary phases including Chiral IG-3, IB N-5, IC, MD (2), MQ (2) and MX (2) used were purchased from Daicel Chiral Technologies (China) Co., Ltd. and Guangzhou FLM Scientific Instrument Co. Ltd. Optical rotations were measured using a Rudolph Autopol I polarimeter.
4.2 General procedure for Rh(III)-catalyzed allylation of olefins with diazo compounds
A 10 mL Schlenk tube with septum containing Rh-1 (2.5 mol%), Cu(OAc)2 (2.0 equiv.) and AgSbF6 (2.0 equiv.) were evacuated and purged with nitrogen gas three times. Followed by this, alkene 1 (3.0 equiv.) and diazo compound 2 (1.0 equiv.) were dissolved in 2,2,2-trifluoroethanol (TFE, 0.5 mL), and the resulting solution was added into the reaction mixture via syringe. Then, rubber septum was taken out and screw cap was used to cover the tube. The reaction mixture was allowed to stir at 25 ℃ for 18 h. The reaction mixture was allowed to reach ambient temperature and diluted with CH2Cl2, followed by filtration through celite and the filtrate was concentrated. The crude residue was purified through a silica gel column chromatography using hexane and ethyl acetate as eluent to give 3 and 3'.
Dibenzyl (R)-2-(oct-1-en-3-yl)malonate (3a) and dibenzyl (E)-2-(oct-2-en-1-yl)malonate (3a'): Yellow oil (28.1 mg, 71% yield, B∶L=3.3∶1, 87% ee). Eluent: V(petro-leum ether)∶V(ethyl acetate)=90∶10. 
－1.04 (c 0.3, acetone); 1H NMR (500 MHz, CDCl3) δ: 7.38~7.26 (m, 13H), 5.68~5.57 (m, 1H), 5.53~5.46 (m, 0.33H), 5.37~5.31 (m, 0.30H), 5.15 (d, J=1.5 Hz, 3H), 5.10 (s, 2H), 5.05~4.98 (m, 2H), 3.52~3.49 (m, 0.36H), 3.47 (d, J=8.8 Hz, 1H), 2.79 (dd J=9.3, 3.7 Hz, 1H), 2.65~2.59 (m, 0.61H), 1.91 (q, J=7.0 Hz, 0.63H), 1.44~1.15 (m, 10H), 0.86 (dt, J=14.1, 7.0 Hz, 4H); 13C NMR (101 MHz, CDCl3) δ: 168.89, 168.25, 168.08, 138.14, 135.55, 135.52, 134.44, 128.66, 128.62, 128.46, 128.44, 128.42, 128.29, 125.02, 117.60, 67.18, 67.16, 67.07, 57.15, 52.46, 44.36, 32.35, 31.64, 26.73, 22.61, 14.15. HRMS (ESI-TOF) calcd for C25H31O4 [M＋H]＋ 395.2222, found 395.2229. HPLC analysis: chiral IG-3 (250 mm×4.6 mm, 3 µm, V(hexa-ne)∶V(i-PrOH)=98∶2, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=32.02 min, tR(major)=33.29 min.
－1.04 (c 0.3, acetone); 1H NMR (500 MHz, CDCl3) δ: 7.38~7.26 (m, 13H), 5.68~5.57 (m, 1H), 5.53~5.46 (m, 0.33H), 5.37~5.31 (m, 0.30H), 5.15 (d, J=1.5 Hz, 3H), 5.10 (s, 2H), 5.05~4.98 (m, 2H), 3.52~3.49 (m, 0.36H), 3.47 (d, J=8.8 Hz, 1H), 2.79 (dd J=9.3, 3.7 Hz, 1H), 2.65~2.59 (m, 0.61H), 1.91 (q, J=7.0 Hz, 0.63H), 1.44~1.15 (m, 10H), 0.86 (dt, J=14.1, 7.0 Hz, 4H); 13C NMR (101 MHz, CDCl3) δ: 168.89, 168.25, 168.08, 138.14, 135.55, 135.52, 134.44, 128.66, 128.62, 128.46, 128.44, 128.42, 128.29, 125.02, 117.60, 67.18, 67.16, 67.07, 57.15, 52.46, 44.36, 32.35, 31.64, 26.73, 22.61, 14.15. HRMS (ESI-TOF) calcd for C25H31O4 [M＋H]＋ 395.2222, found 395.2229. HPLC analysis: chiral IG-3 (250 mm×4.6 mm, 3 µm, V(hexa-ne)∶V(i-PrOH)=98∶2, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=32.02 min, tR(major)=33.29 min.Dibenzyl (R)-2-(but-3-en-2-yl)malonate (3b) and dibenzyl (E)-2-(but-2-en-1-yl)malonate (3b'): Yellow oil (19.2 mg, 65% yield, B∶L=3∶1, 85% ee). Eluent: V(petroleum ether)∶V(ethyl acetate)=90∶10. 
＋4.32 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.38~7.27 (m, 13H), 5.83~5.71 (m, 1H), 5.55~5.44 (m, 0.32H), 5.39~5.32 (m, 0.38H), 5.15 (s, 3H), 5.11 (s, 2H), 5.04 (dt, J=17.1, 1.3 Hz, 1H), 4.97 (dt, J=10.4, 1.1 Hz, 1H), 3.49 (t, J=7.6 Hz, 0.32H), 3.41 (d, J=8.8 Hz, 1H), 3.06~2.94 (m, 1H), 2.61 (td, J=7.2, 1.3 Hz, 0.64H), 1.58 (dt, J=2.8, 1.29 Hz, 1H), 1.08 (d, J=6.8 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 168.9, 168.1, 168.1, 139.7, 135.5, 135.5, 128.8, 128.7, 128.6, 128.5, 128.4, 128.4, 128.4, 128.3, 126.3, 115.7, 67.2, 67.1, 57.8, 52.4, 38.2, 32.0, 18.1, 18.0. HRMS (ESI-TOF) calcd for C21H23O4Na [M＋Na]＋ 361.1416, found 361.1415. HPLC analysis: chiral IC (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=99∶1, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=34.19 min, tR(major)=34.10 min.
＋4.32 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.38~7.27 (m, 13H), 5.83~5.71 (m, 1H), 5.55~5.44 (m, 0.32H), 5.39~5.32 (m, 0.38H), 5.15 (s, 3H), 5.11 (s, 2H), 5.04 (dt, J=17.1, 1.3 Hz, 1H), 4.97 (dt, J=10.4, 1.1 Hz, 1H), 3.49 (t, J=7.6 Hz, 0.32H), 3.41 (d, J=8.8 Hz, 1H), 3.06~2.94 (m, 1H), 2.61 (td, J=7.2, 1.3 Hz, 0.64H), 1.58 (dt, J=2.8, 1.29 Hz, 1H), 1.08 (d, J=6.8 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 168.9, 168.1, 168.1, 139.7, 135.5, 135.5, 128.8, 128.7, 128.6, 128.5, 128.4, 128.4, 128.4, 128.3, 126.3, 115.7, 67.2, 67.1, 57.8, 52.4, 38.2, 32.0, 18.1, 18.0. HRMS (ESI-TOF) calcd for C21H23O4Na [M＋Na]＋ 361.1416, found 361.1415. HPLC analysis: chiral IC (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=99∶1, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=34.19 min, tR(major)=34.10 min.Dibenzyl (R)-2-(hex-1-en-3-yl)malonate (3c) and dibenzyl (E)-2-(hex-2-en-1-yl)malonate (3c'): Yellow oil (25.4 mg, 72% yield, B∶L=4.8∶1, 88% ee). Eluent: V(petroleum ether)∶V(ethyl acetate)=90∶10; 
－1.37 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.37~7.27 (m, 12H), 5.69~5.56 (m, 1H), 5.54~5.44 (m, 0.25H), 5.39~5.27 (m, 0.25H), 5.20~5.13 (m, 3H), 5.10 (s, 2H), 5.05~4.98 (m, 2H), 3.50 (t, J=7.6 Hz, 0.22H), 3.46 (d, J=8.8 Hz, 1H), 2.81 (d, J=1.3 Hz, 1H), 2.66~2.59 (m, 0.41H), 1.90 (q, J=7.2, 9.2 Hz, 0.45H), 1.42~1.14 (m, 5H), 0.86 (d, J=7.4 Hz, 0.60H), 0.84~0.79 (m, 3H); 13C NMR (101 MHz, CDCl3) δ: 168.9, 168.2, 168.1, 138.1, 135.5, 135.5, 134.2, 128.7, 128.6, 128.5, 128.5, 128.4, 128.4, 128.3, 125.3, 117.6, 67.2, 67.1, 57.1, 52.5, 44.1, 34.6, 34.5, 32.0, 22.5, 20.2, 13.9, 13.7. HRMS (ESI-TOF) calcd for C23H27O4 [M＋H]＋ 367.1909, found 367.1912. HPLC analysis: chiral IC (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=99∶1, 1.0 mL/min, 25 ℃, 210 nm), tR(minor)=13.33 min, tR(major)=14.67 min.
－1.37 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.37~7.27 (m, 12H), 5.69~5.56 (m, 1H), 5.54~5.44 (m, 0.25H), 5.39~5.27 (m, 0.25H), 5.20~5.13 (m, 3H), 5.10 (s, 2H), 5.05~4.98 (m, 2H), 3.50 (t, J=7.6 Hz, 0.22H), 3.46 (d, J=8.8 Hz, 1H), 2.81 (d, J=1.3 Hz, 1H), 2.66~2.59 (m, 0.41H), 1.90 (q, J=7.2, 9.2 Hz, 0.45H), 1.42~1.14 (m, 5H), 0.86 (d, J=7.4 Hz, 0.60H), 0.84~0.79 (m, 3H); 13C NMR (101 MHz, CDCl3) δ: 168.9, 168.2, 168.1, 138.1, 135.5, 135.5, 134.2, 128.7, 128.6, 128.5, 128.5, 128.4, 128.4, 128.3, 125.3, 117.6, 67.2, 67.1, 57.1, 52.5, 44.1, 34.6, 34.5, 32.0, 22.5, 20.2, 13.9, 13.7. HRMS (ESI-TOF) calcd for C23H27O4 [M＋H]＋ 367.1909, found 367.1912. HPLC analysis: chiral IC (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=99∶1, 1.0 mL/min, 25 ℃, 210 nm), tR(minor)=13.33 min, tR(major)=14.67 min.Dibenzyl (R)-2-(dec-1-en-3-yl)malonate (3d) and diben-zyl (E)-2-(dec-2-en-1-yl)malonate (3d'): Yellow oil (27.3 mg, 77% yield, B∶L=4∶1, 87% ee). Eluent: V(petroleum ether)∶V(ethyl acetate)=90∶10. 
－17.32 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.37~7.27 (m, 12H), 5.69~5.57 (m, 1H), 5.53~5.45 (m, 0.29H), 5.37~5.28 (m, 0.33H), 5.15 (d, J=2.0 Hz, 3H), 5.10 (s, 2H), 5.05~5.01 (m, 1H), 5.00 (s, 1H), 3.51 (d, J=7.6 Hz, 0.18H), 3.47 (d, J=8.7 Hz, 1H), 2.79 (q, J=9.2, 1H), 2.65~2.58 (m, 0.51H), 1.91 (q, J=5.2 Hz, 0.58H), 1.46~1.36 (m, 1H), 1.32~1.14 (m, 14H), 0.87 (t, J=7.0 Hz, 4H); 13C NMR (101 MHz, CDCl3) δ: 168.9, 168.2, 168.1, 138.1, 135.5, 135.5, 134.4, 128.7, 128.6, 128.5, 128.5, 128.4, 128.4, 128.3, 125.0, 117.6, 67.2, 67.2, 67.1, 57.1, 52.5, 44.4, 32.6, 32.4, 32.0, 31.9, 29.4, 29.3, 29.2, 27.1, 22.8, 22.8, 14.2. HRMS (ESI-TOF) calcd for C27H33O4 [M－H]＋ 421.2386, found 421.2384. HPLC analysis: chiral IG-3 (250 mm×4.6 mm, 3 µm, V(he-xane)∶V(i-PrOH)=99∶1, 1.0 mL/min, 25 ℃, 210 nm), tR(minor)=29.27 min, tR(major)=34.27 min.
－17.32 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.37~7.27 (m, 12H), 5.69~5.57 (m, 1H), 5.53~5.45 (m, 0.29H), 5.37~5.28 (m, 0.33H), 5.15 (d, J=2.0 Hz, 3H), 5.10 (s, 2H), 5.05~5.01 (m, 1H), 5.00 (s, 1H), 3.51 (d, J=7.6 Hz, 0.18H), 3.47 (d, J=8.7 Hz, 1H), 2.79 (q, J=9.2, 1H), 2.65~2.58 (m, 0.51H), 1.91 (q, J=5.2 Hz, 0.58H), 1.46~1.36 (m, 1H), 1.32~1.14 (m, 14H), 0.87 (t, J=7.0 Hz, 4H); 13C NMR (101 MHz, CDCl3) δ: 168.9, 168.2, 168.1, 138.1, 135.5, 135.5, 134.4, 128.7, 128.6, 128.5, 128.5, 128.4, 128.4, 128.3, 125.0, 117.6, 67.2, 67.2, 67.1, 57.1, 52.5, 44.4, 32.6, 32.4, 32.0, 31.9, 29.4, 29.3, 29.2, 27.1, 22.8, 22.8, 14.2. HRMS (ESI-TOF) calcd for C27H33O4 [M－H]＋ 421.2386, found 421.2384. HPLC analysis: chiral IG-3 (250 mm×4.6 mm, 3 µm, V(he-xane)∶V(i-PrOH)=99∶1, 1.0 mL/min, 25 ℃, 210 nm), tR(minor)=29.27 min, tR(major)=34.27 min.Dibenzyl (R)-2-(4-methylpent-1-en-3-yl)malonate (3e) and dibenzyl (E)-2-(4-methylpent-2-en-1-yl)malonate (3e'): Yellow oil (21.1 mg, 65% yield, B∶L=1.1∶1, 86% ee). Eluent: V(petroleum ether)∶V(ethyl acetate)=90∶10. 
－7.12 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.38~7.26 (m, 21H), 5.69 (dt, J=17.0, 10.1 Hz, 1H), 5.53~5.43 (m, 1H), 5.35~5.25 (m, 1H), 5.15 (s, 6H), 5.10 (s, 2H), 5.08~4.97 (m, 2H), 3.67 (d, J=9.5 Hz, 1H), 3.51 (t, J=7.6 Hz, 1H), 2.70 (td, J=9.7, 5.1 Hz, 1H), 2.62 (td, J=7.2, 1.0 Hz, 2.26H), 2.24~2.13 (m, 1.13H), 1.73 (pd, J=6.8, 5.0 Hz, 1.05H), 0.91 (d, J=6.8 Hz, 7H), 0.88 (d, J=6.7 Hz, 3H), 0.82 (d, J=6.8 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 168.9, 168.4, 168.1, 141.3, 135.6, 134.8, 128.7, 128.6, 128.6, 128.5, 128.4, 128.4, 128.4, 128.3, 122.1, 118.9, 67.2, 67.1, 67.1, 55.1, 52.5, 50.5, 31.9, 31.0, 29.1, 22.4, 21.3, 17.7. HRMS (ESI-TOF) calcd for C23H26-NO4 [M＋NH4]＋ 384.2175, found 384.2170. HPLC analysis: chiral MQ (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=95∶5, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=29.35 min, tR(major)=34.14 min.
－7.12 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.38~7.26 (m, 21H), 5.69 (dt, J=17.0, 10.1 Hz, 1H), 5.53~5.43 (m, 1H), 5.35~5.25 (m, 1H), 5.15 (s, 6H), 5.10 (s, 2H), 5.08~4.97 (m, 2H), 3.67 (d, J=9.5 Hz, 1H), 3.51 (t, J=7.6 Hz, 1H), 2.70 (td, J=9.7, 5.1 Hz, 1H), 2.62 (td, J=7.2, 1.0 Hz, 2.26H), 2.24~2.13 (m, 1.13H), 1.73 (pd, J=6.8, 5.0 Hz, 1.05H), 0.91 (d, J=6.8 Hz, 7H), 0.88 (d, J=6.7 Hz, 3H), 0.82 (d, J=6.8 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 168.9, 168.4, 168.1, 141.3, 135.6, 134.8, 128.7, 128.6, 128.6, 128.5, 128.4, 128.4, 128.4, 128.3, 122.1, 118.9, 67.2, 67.1, 67.1, 55.1, 52.5, 50.5, 31.9, 31.0, 29.1, 22.4, 21.3, 17.7. HRMS (ESI-TOF) calcd for C23H26-NO4 [M＋NH4]＋ 384.2175, found 384.2170. HPLC analysis: chiral MQ (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=95∶5, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=29.35 min, tR(major)=34.14 min.Dibenzyl (R)-2-(1-cyclohexylallyl)malonate (3f) and dibenzyl (E)-2-(3-cyclohexylallyl)malonate (3f'): Yellow oil (18.7 mg, 45% yield, B∶L=1∶1.5, 92% ee). Eluent: V(petroleum ether)∶V(ethyl acetate)=90∶10. 
－8.19 (c 0.3, acetone); 1H NMR (500 MHz, CDCl3) δ: 7.34~7.28 (m, 25H), 5.72 (dt, J=17.0, 10.1 Hz, 1H), 5.50~5.41 (m, 1.51H), 5.35~5.25 (m, 1.64H), 5.15 (s, 8H), 5.11 (d, J=3.8 Hz, 2H), 5.03~4.93 (m, 2H), 3.71 (d, J=9.2 Hz, 1H), 3.50 (t, J=7.6 Hz, 1.47H), 2.67 (td, J=9.5, 5.5 Hz, 1H), 2.61 (t, J=7.2 Hz, 3H), 1.88~1.79 (m, 1.55H), 1.71~1.61 (m, 11H), 1.28~0.82 (m, 15H); 13C NMR (101 MHz, CDCl3) δ: 168.9, 168.6, 168.2, 140.2, 135.8, 135.6, 128.7, 128.6, 128.5, 128.5, 128.4, 128.4, 128.3, 122.6, 118.5, 67.2, 67.1, 67.0, 54.5, 52.6, 50.3, 40.6, 39.1, 33.0, 32.1, 31.6, 28.6, 26.4, 26.3, 26.2, 26.1. HRMS (ESI-TOF) calcd for C26H31O4 [M＋H]＋ 407.2222, found 407.2230. HPLC analysis: chiral MX (2) (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-Pr-OH)=95∶5, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=13.74 min, tR(major)=15.70 min.
－8.19 (c 0.3, acetone); 1H NMR (500 MHz, CDCl3) δ: 7.34~7.28 (m, 25H), 5.72 (dt, J=17.0, 10.1 Hz, 1H), 5.50~5.41 (m, 1.51H), 5.35~5.25 (m, 1.64H), 5.15 (s, 8H), 5.11 (d, J=3.8 Hz, 2H), 5.03~4.93 (m, 2H), 3.71 (d, J=9.2 Hz, 1H), 3.50 (t, J=7.6 Hz, 1.47H), 2.67 (td, J=9.5, 5.5 Hz, 1H), 2.61 (t, J=7.2 Hz, 3H), 1.88~1.79 (m, 1.55H), 1.71~1.61 (m, 11H), 1.28~0.82 (m, 15H); 13C NMR (101 MHz, CDCl3) δ: 168.9, 168.6, 168.2, 140.2, 135.8, 135.6, 128.7, 128.6, 128.5, 128.5, 128.4, 128.4, 128.3, 122.6, 118.5, 67.2, 67.1, 67.0, 54.5, 52.6, 50.3, 40.6, 39.1, 33.0, 32.1, 31.6, 28.6, 26.4, 26.3, 26.2, 26.1. HRMS (ESI-TOF) calcd for C26H31O4 [M＋H]＋ 407.2222, found 407.2230. HPLC analysis: chiral MX (2) (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-Pr-OH)=95∶5, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=13.74 min, tR(major)=15.70 min.Dibenzyl (R)-2-(1-phenylallyl)malonate (3g) and diben-zyl 2-cinnamylmalonate (3g'): Yellow oil (24.2 mg, 61% yield, B∶L=1∶1, 75% ee). Eluent: V(petroleum ether)∶V(ethyl acetate)=90∶10; 
－7.17 (c 0.3, acetone); 1H NMR (500 MHz, CDCl3) δ: 7.38~7.20 (m, 20 H), 7.16 (d, J=8.0 Hz, 2H), 7.12~7.02 (m, 8H), 6.41 (d, J=15.8 Hz, 1H), 6.12~6.01 (m, 1H), 6.02~5.93 (m, 1H), 5.16 (d, J=3.5 Hz, 6H), 5.09~4.98 (m, 2H), 4.91 (s, 2H), 4.14~4.05 (m, 1H), 3.94 (d, J=11.0 Hz, 1H), 3.61 (t, J=7.5 Hz, 1H), 2.87~2.77 (m, 2H), 2.32 (d, J=14.2 Hz, 6H); 13C NMR (126 MHz, CDCl3) δ: 168.8, 167.7, 167.4, 138.0, 137.3, 137.0, 136.8, 135.5, 135.4, 135.3, 134.3, 133.0, 129.5, 129.3, 128.7, 128.7, 128.5, 128.5, 128.4, 128.3, 128.2, 127.9, 126.3, 124.3, 116.6, 67.4, 67.3, 67.2, 57.6, 52.3, 49.5, 32.4, 21.3, 21.2. HRMS (ESI-TOF) calcd for C26H25O4 [M＋H]＋ 401.1753, found 401.1759. HPLC analysis: chiral IC (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=99∶1, 0.5 mL/min, 25 ℃, 210 nm), tR(mi-nor)=40.52 min, tR(major)=42.91 min.
－7.17 (c 0.3, acetone); 1H NMR (500 MHz, CDCl3) δ: 7.38~7.20 (m, 20 H), 7.16 (d, J=8.0 Hz, 2H), 7.12~7.02 (m, 8H), 6.41 (d, J=15.8 Hz, 1H), 6.12~6.01 (m, 1H), 6.02~5.93 (m, 1H), 5.16 (d, J=3.5 Hz, 6H), 5.09~4.98 (m, 2H), 4.91 (s, 2H), 4.14~4.05 (m, 1H), 3.94 (d, J=11.0 Hz, 1H), 3.61 (t, J=7.5 Hz, 1H), 2.87~2.77 (m, 2H), 2.32 (d, J=14.2 Hz, 6H); 13C NMR (126 MHz, CDCl3) δ: 168.8, 167.7, 167.4, 138.0, 137.3, 137.0, 136.8, 135.5, 135.4, 135.3, 134.3, 133.0, 129.5, 129.3, 128.7, 128.7, 128.5, 128.5, 128.4, 128.3, 128.2, 127.9, 126.3, 124.3, 116.6, 67.4, 67.3, 67.2, 57.6, 52.3, 49.5, 32.4, 21.3, 21.2. HRMS (ESI-TOF) calcd for C26H25O4 [M＋H]＋ 401.1753, found 401.1759. HPLC analysis: chiral IC (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=99∶1, 0.5 mL/min, 25 ℃, 210 nm), tR(mi-nor)=40.52 min, tR(major)=42.91 min.Dibenzyl (R)-2-(1-phenylbut-3-en-2-yl)malonate (3h) and dibenzyl (E)-2-(4-phenylbut-2-en-1-yl) malonate (3h'): Yellow oil (13.2 mg, 32% yield, B∶L=5∶1, 80% ee). Eluent: V(petroleum ether)∶V(ethyl acetate)=90∶10. 
＋11.43 (c 0.3, acetone); 1H NMR (500 MHz, CDCl3) δ: 7.35~7.28 (m, 12H), 7.25~7.14 (m, 5H), 7.09~7.02 (m, 2H), 5.80~5.69 (m, 1H), 5.67~5.61 (m, 0.21H), 5.47~5.19 (m, 0.19H), 5.15~5.09 (m, 5H), 4.98~4.81 (m, 2H), 3.52 (d, J=7.8 Hz, 1H), 3.17~3.16 (m, 0.07 H) 3.15~3.05 (m, 1H), 2.87~2.79 (m, 1H), 2.70~2.59 (m, 2H); 13C NMR (126 MHz, CDCl3) δ: 168.3, 168.0, 139.0, 137.2, 129.5, 128.7, 128.7, 128.7, 128.6, 128.6, 128.5, 128.5, 128.5, 128.3, 128.3, 126.4, 117.8, 67.3, 67.2, 55.9, 45.7, 38.9. HRMS (ESI-TOF) calcd for C27H25O4 [M－H]＋ 413.1758, found 413.156. HPLC analysis: chiral IG-3 (250 mm×4.6 mm, 3 µm, V(hexane)∶V(i-PrOH)=95∶5, 1.0 mL/min, 25 ℃, 210 nm), tR(minor)=10.45 min, tR(major)=11.38 min.
＋11.43 (c 0.3, acetone); 1H NMR (500 MHz, CDCl3) δ: 7.35~7.28 (m, 12H), 7.25~7.14 (m, 5H), 7.09~7.02 (m, 2H), 5.80~5.69 (m, 1H), 5.67~5.61 (m, 0.21H), 5.47~5.19 (m, 0.19H), 5.15~5.09 (m, 5H), 4.98~4.81 (m, 2H), 3.52 (d, J=7.8 Hz, 1H), 3.17~3.16 (m, 0.07 H) 3.15~3.05 (m, 1H), 2.87~2.79 (m, 1H), 2.70~2.59 (m, 2H); 13C NMR (126 MHz, CDCl3) δ: 168.3, 168.0, 139.0, 137.2, 129.5, 128.7, 128.7, 128.7, 128.6, 128.6, 128.5, 128.5, 128.5, 128.3, 128.3, 126.4, 117.8, 67.3, 67.2, 55.9, 45.7, 38.9. HRMS (ESI-TOF) calcd for C27H25O4 [M－H]＋ 413.1758, found 413.156. HPLC analysis: chiral IG-3 (250 mm×4.6 mm, 3 µm, V(hexane)∶V(i-PrOH)=95∶5, 1.0 mL/min, 25 ℃, 210 nm), tR(minor)=10.45 min, tR(major)=11.38 min.Dibenzyl (R)-2-(7-phenylhept-1-en-3-yl)malonate (3i) and dibenzyl (E)-2-(4-phenylhept-2-en-1-yl)malonate (3i'): Yellow oil (26.2 mg, 65% yield, B∶L=1.5∶1, 73% ee). Eluent: V(petroleum ether)∶V(ethyl acetate)=90∶10. 
＋12.76 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.36~7.22 (m, 20H), 7.21~7.10 (m, 5H), 5.67~5.55 (m, 1H), 5.52~5.42 (m, 0.69H), 5.36~5.29 (m, 0.69H), 5.14 (d, J=1.3 Hz, 2H), 5.12 (d, J=3.0 Hz, 2H), 5.09 (s, 2H), 5.04~4.99 (m, 1H), 4.98 (s, 1H), 3.49 (t, J=7.7 Hz, 0.65H), 3.46 (d, J=8.8 Hz, 1H), 2.78 (q, J=9.2, 1H), 2.59 (dt, J=15.6, 7.8 Hz, 3H), 2.54~2.49 (m, 1.49H), 1.94 (q, J=7.1 Hz, 1.30H), 1.57~1.48 (m, 3H), 1.47~1.40 (m, 1H), 1.39~1.28 (m, 4H); 13C NMR (101 MHz, CDCl3) δ: 168.9, 168.2, 168.0, 142.7, 138.0, 135.5, 135.5, 135.5, 134.1, 128.7, 128.6, 128.5, 128.5, 128.5, 128.4, 128.4, 128.4, 128.3, 125.7, 125.3, 117.7, 67.2, 67.2, 67.1, 57.1, 52.4, 44.2, 35.9, 35.9, 32.4, 32.2, 32.0, 31.2, 31.0, 29.0, 26.7. HRMS (ESI-TOF) calcd for C30H31O4 [M＋H]＋ 455.2227, found 455.2229. HPLC analysis: chiral IC (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=99∶1, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=41.17 min, tR(major)=43.73 min.
＋12.76 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.36~7.22 (m, 20H), 7.21~7.10 (m, 5H), 5.67~5.55 (m, 1H), 5.52~5.42 (m, 0.69H), 5.36~5.29 (m, 0.69H), 5.14 (d, J=1.3 Hz, 2H), 5.12 (d, J=3.0 Hz, 2H), 5.09 (s, 2H), 5.04~4.99 (m, 1H), 4.98 (s, 1H), 3.49 (t, J=7.7 Hz, 0.65H), 3.46 (d, J=8.8 Hz, 1H), 2.78 (q, J=9.2, 1H), 2.59 (dt, J=15.6, 7.8 Hz, 3H), 2.54~2.49 (m, 1.49H), 1.94 (q, J=7.1 Hz, 1.30H), 1.57~1.48 (m, 3H), 1.47~1.40 (m, 1H), 1.39~1.28 (m, 4H); 13C NMR (101 MHz, CDCl3) δ: 168.9, 168.2, 168.0, 142.7, 138.0, 135.5, 135.5, 135.5, 134.1, 128.7, 128.6, 128.5, 128.5, 128.5, 128.4, 128.4, 128.4, 128.3, 125.7, 125.3, 117.7, 67.2, 67.2, 67.1, 57.1, 52.4, 44.2, 35.9, 35.9, 32.4, 32.2, 32.0, 31.2, 31.0, 29.0, 26.7. HRMS (ESI-TOF) calcd for C30H31O4 [M＋H]＋ 455.2227, found 455.2229. HPLC analysis: chiral IC (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=99∶1, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=41.17 min, tR(major)=43.73 min.Dibenzyl (R)-2-(7-(thiophen-2-yl)hept-1-en-3-yl)-malo-nate (3j) and dibenzyl (E)-2-(7-(thiophen-2-yl)hept-2-en-1-yl)malonate (3j'): Yellow oil (23.7 mg, 52% yield, B∶L=3∶1, 72% ee). Eluent: V(petroleum ether)∶ V(ethyl acetate)=90∶10. 
＋6.02 (c 0.3, acetone); 1H NMR (500 MHz, CDCl3) δ: 7.37~7.26 (m, 17H), 7.14~7.05 (m, 2H), 6.97~6.88 (m, 2H), 6.82~6.71 (m, 2H), 5.69~5.58 (m, 1H), 5.51~5.42 (m, 0.35H), 5.38~5.31 (m, 0.49H), 5.17~5.10 (m, 6H), 5.07~4.99 (m, 2H), 3.51 (t, J=7.6 Hz, 0.38H), 3.47 (d, J=8.7 Hz, 1H), 2.84~2.72 (m, 4H), 2.63 (t, J=7.2 Hz, 1H), 2.00~1.92 (m, 1H), 1.65~1.57 (m, 3H), 1.50~1.20 (m, 8H); 13C NMR (101 MHz, CDCl3) δ: 168.8, 168.2, 168.0, 145.5, 137.9, 135.5, 135.5, 135.5, 133.9, 128.7, 128.7, 128.6, 128.6, 128.5, 128.5, 128.4, 128.3, 128.3, 128.1, 126.8, 126.8, 125.4, 124.1, 124.1, 122.9, 117.8, 67.2, 67.2, 67.1, 57.1, 52.4, 44.2, 32.2, 32.0, 32.0, 31.5, 31.3, 29.9, 29.8, 29.8, 28.7, 26.5. HRMS (ESI-TOF) calcd for C28H31O4S [M＋H]＋ 463.1943, found 463.1944. HPLC analysis: chiral IC (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=99∶1, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=50.17 min, tR(major)=53.21 min.
＋6.02 (c 0.3, acetone); 1H NMR (500 MHz, CDCl3) δ: 7.37~7.26 (m, 17H), 7.14~7.05 (m, 2H), 6.97~6.88 (m, 2H), 6.82~6.71 (m, 2H), 5.69~5.58 (m, 1H), 5.51~5.42 (m, 0.35H), 5.38~5.31 (m, 0.49H), 5.17~5.10 (m, 6H), 5.07~4.99 (m, 2H), 3.51 (t, J=7.6 Hz, 0.38H), 3.47 (d, J=8.7 Hz, 1H), 2.84~2.72 (m, 4H), 2.63 (t, J=7.2 Hz, 1H), 2.00~1.92 (m, 1H), 1.65~1.57 (m, 3H), 1.50~1.20 (m, 8H); 13C NMR (101 MHz, CDCl3) δ: 168.8, 168.2, 168.0, 145.5, 137.9, 135.5, 135.5, 135.5, 133.9, 128.7, 128.7, 128.6, 128.6, 128.5, 128.5, 128.4, 128.3, 128.3, 128.1, 126.8, 126.8, 125.4, 124.1, 124.1, 122.9, 117.8, 67.2, 67.2, 67.1, 57.1, 52.4, 44.2, 32.2, 32.0, 32.0, 31.5, 31.3, 29.9, 29.8, 29.8, 28.7, 26.5. HRMS (ESI-TOF) calcd for C28H31O4S [M＋H]＋ 463.1943, found 463.1944. HPLC analysis: chiral IC (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=99∶1, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=50.17 min, tR(major)=53.21 min.Dibenzyl (R)-2-(6-chlorohex-1-en-3-yl)malonate (3k) and dibenzyl (E)-2-(6-chlorohex-2-en-1-yl)malonate (3k'): Yellow oil (18.9 mg, 47% yield, B∶L=2∶1, 77% ee). Eluent: V(petroleum ether)∶V(ethyl acetate)=90∶10. 
＋6.82 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.38~7.27 (m, 14H), 5.62 (dt, J=17.4, 9.5 Hz, 1H), 5.42 (q, J=5.5 Hz, 1H), 5.16 (s, 2H), 5.15 (d, J=1.2 Hz, 2H), 5.11 (s, 2H), 5.08~5.00 (m, 2H), 3.54~3.36 (m, 4.41H), 2.80 (q, J=9.2, 1H), 2.67~2.59 (m, 1H), 2.07 (q, J=6.4, 1H), 1.84~1.72 (m, 2H), 1.70~1.63 (m, 1H), 1.59~1.53 (m, 1H), 1.47~1.37 (m, 1H); 13C NMR (101 MHz, CDCl3) δ: 168.7, 168.0, 167.8, 137.4, 135.5, 135.4, 132.1, 128.7, 128.6, 128.5, 128.5, 128.5, 128.3, 126.8, 118.4, 67.3, 67.2, 67.2, 57.0, 52.2, 44.7, 44.3, 43.8, 31.9, 31.9, 30.3, 29.6, 29.5. HRMS (ESI-TOF) calcd for C23H24ClO4 [M－H]＋ 399.1368, found 399.1370. HPLC analysis: chiral IG-3 (250 mm×4.6 mm, 3 µm, V(hexane)∶V(i-PrOH)=98∶2, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=20.54 min, tR(major)=21.86 min.
＋6.82 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.38~7.27 (m, 14H), 5.62 (dt, J=17.4, 9.5 Hz, 1H), 5.42 (q, J=5.5 Hz, 1H), 5.16 (s, 2H), 5.15 (d, J=1.2 Hz, 2H), 5.11 (s, 2H), 5.08~5.00 (m, 2H), 3.54~3.36 (m, 4.41H), 2.80 (q, J=9.2, 1H), 2.67~2.59 (m, 1H), 2.07 (q, J=6.4, 1H), 1.84~1.72 (m, 2H), 1.70~1.63 (m, 1H), 1.59~1.53 (m, 1H), 1.47~1.37 (m, 1H); 13C NMR (101 MHz, CDCl3) δ: 168.7, 168.0, 167.8, 137.4, 135.5, 135.4, 132.1, 128.7, 128.6, 128.5, 128.5, 128.5, 128.3, 126.8, 118.4, 67.3, 67.2, 67.2, 57.0, 52.2, 44.7, 44.3, 43.8, 31.9, 31.9, 30.3, 29.6, 29.5. HRMS (ESI-TOF) calcd for C23H24ClO4 [M－H]＋ 399.1368, found 399.1370. HPLC analysis: chiral IG-3 (250 mm×4.6 mm, 3 µm, V(hexane)∶V(i-PrOH)=98∶2, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=20.54 min, tR(major)=21.86 min.Dibenzyl (R)-2-(6-bromohex-1-en-3-yl)malonate (3l) and dibenzyl (E)-2-(6-bromohex-2-en-1-yl)malonate (3l'): Yellow oil (26.3 mg, 67% yield, B∶L=6.7∶1, 72% ee). Eluent: V(petroleum ether)∶V(ethyl acetate)=90∶10. 
＋19.70 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.36~7.30 (m, 15H), 5.62 (dt, J=17.4, 9.6 Hz, 1H), 5.44~5.38 (m, 1H), 5.15 (d, J=4.3 Hz, 3H), 5.11 (s, 2H), 5.04 (q, J=13.6, 2H), 3.51 (d, J=7.6 Hz, 0.25H), 3.49~3.45 (m, 1H), 3.37~3.23 (m, 3H), 3.00 (d, J=5.3 Hz, 0.46H), 2.80 (q, J=9.3, 1H), 2.65~2.60 (m, 0.48H), 2.12~2.03 (m, 1H), 1.91~1.80 (m, 2H), 1.79~1.70 (m, 1H), 1.59~1.52 (m, 1H), 1.48~1.36 (m, 1H); 13C NMR (101 MHz, CDCl3) δ: 167.96, 167.81, 137.37, 135.40, 128.71, 128.65, 128.56, 128.51, 128.35, 118.42, 67.35, 67.23, 56.98, 43.73, 33.33, 30.89, 30.52. HRMS (ESI-TOF) calcd for C23H26BrO4 [M＋H]＋ 443.0863, found 443.0865. HPLC analysis: chiral IC (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=99∶1, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=57.07 min, tR(major)=57.68 min.
＋19.70 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.36~7.30 (m, 15H), 5.62 (dt, J=17.4, 9.6 Hz, 1H), 5.44~5.38 (m, 1H), 5.15 (d, J=4.3 Hz, 3H), 5.11 (s, 2H), 5.04 (q, J=13.6, 2H), 3.51 (d, J=7.6 Hz, 0.25H), 3.49~3.45 (m, 1H), 3.37~3.23 (m, 3H), 3.00 (d, J=5.3 Hz, 0.46H), 2.80 (q, J=9.3, 1H), 2.65~2.60 (m, 0.48H), 2.12~2.03 (m, 1H), 1.91~1.80 (m, 2H), 1.79~1.70 (m, 1H), 1.59~1.52 (m, 1H), 1.48~1.36 (m, 1H); 13C NMR (101 MHz, CDCl3) δ: 167.96, 167.81, 137.37, 135.40, 128.71, 128.65, 128.56, 128.51, 128.35, 118.42, 67.35, 67.23, 56.98, 43.73, 33.33, 30.89, 30.52. HRMS (ESI-TOF) calcd for C23H26BrO4 [M＋H]＋ 443.0863, found 443.0865. HPLC analysis: chiral IC (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=99∶1, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=57.07 min, tR(major)=57.68 min.Dibenzyl (R)-2-(7-bromohept-1-en-3-yl)malonate (3m) and dibenzyl (E)-2-(7-bromohept-2-en-1-yl) malonate (3m'): Yellow oil (22.9 mg, 49% yield, B∶L=20∶1, 71% ee). Eluent: V(petroleum ether)∶V(ethyl acetate)=90∶10. 
－4.11 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.37~7.25 (m, 11H), 5.68~5.54 (m, 1H), 5.21~5.17 (m, 0.22H), 5.15 (d, J=1.2 Hz, 2H), 5.11 (s, 2H), 5.09~5.02 (m, 1H), 5.02 (s, 1H), 3.51 (d, J=7.3 Hz, 0.06H), 3.46 (d, J=8.7 Hz, 1H), 3.37 (d, J=6.8 Hz, 0.20H), 3.32 (td, J=6.8, 1.3 Hz, 2H), 2.85~2.73 (m, 1H), 2.62 (t,J=7.0 Hz, 0.10H), 1.95 (q, J=7.0 Hz, 0.11H), 1.85~1.67 (m, 2H), 1.48~1.38 (m, 2H), 1.30 (q, J=2.6 Hz, 2H); 13C NMR (101 MHz, CDCl3) δ: 168.1, 167.9, 137.6, 135.4, 135.4, 128.7, 128.7, 128.6, 128.5, 128.5, 128.5, 128.5, 118.1, 67.2, 67.1, 57.0, 44.1, 33.6, 32.4, 31.3, 25.6. HRMS (ESI-TOF) calcd for C24H26BrO4 [M－H]＋ 457.1020, found 457.1021. HPLC analysis: chiral IC (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=99∶1, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=32.87 min, tR(major)=35.33 min.
－4.11 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.37~7.25 (m, 11H), 5.68~5.54 (m, 1H), 5.21~5.17 (m, 0.22H), 5.15 (d, J=1.2 Hz, 2H), 5.11 (s, 2H), 5.09~5.02 (m, 1H), 5.02 (s, 1H), 3.51 (d, J=7.3 Hz, 0.06H), 3.46 (d, J=8.7 Hz, 1H), 3.37 (d, J=6.8 Hz, 0.20H), 3.32 (td, J=6.8, 1.3 Hz, 2H), 2.85~2.73 (m, 1H), 2.62 (t,J=7.0 Hz, 0.10H), 1.95 (q, J=7.0 Hz, 0.11H), 1.85~1.67 (m, 2H), 1.48~1.38 (m, 2H), 1.30 (q, J=2.6 Hz, 2H); 13C NMR (101 MHz, CDCl3) δ: 168.1, 167.9, 137.6, 135.4, 135.4, 128.7, 128.7, 128.6, 128.5, 128.5, 128.5, 128.5, 118.1, 67.2, 67.1, 57.0, 44.1, 33.6, 32.4, 31.3, 25.6. HRMS (ESI-TOF) calcd for C24H26BrO4 [M－H]＋ 457.1020, found 457.1021. HPLC analysis: chiral IC (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=99∶1, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=32.87 min, tR(major)=35.33 min.Dibenzyl (R)-2-(10-hydroxydec-1-en-3-yl)malonate (3n) and dibenzyl (E)-2-(10-hydroxydec-2-en-1-yl)malonate (3n'): Yellow oil (26.5 mg, 66% yield, B∶L=2.5∶1, 73% ee). Eluent: V(petroleum ether)∶V(ethyl acetate)=90∶10. 
＋30.35 (c 0.3, acetone); 1H NMR (500 MHz, CDCl3) δ: 7.35~7.27 (m, 14H), 5.67~5.57 (m, 1H), 5.52~5.45 (m, 0.42H), 5.37~5.30 (m, 0.45H), 5.14 (dd, J=3.1, 1.5 Hz, 3H), 5.10 (s, 2H), 5.05~5.01 (m, 1H), 5.00 (s, 1H), 3.62 (td, J=6.6, 2.6 Hz, 2.82H), 3.50 (t, J=7.6 Hz, 0.42H), 3.46 (d, J=8.8 Hz, 1H), 2.78 (q, J=9.3 Hz, 1H), 2.62 (t, J=7.2 Hz, 0.80H), 1.91 (q, J=6.7 Hz, 0.87H), 1.58~1.51 (m, 4H), 1.35~1.21 (m, 12H); 13C NMR (126 MHz, CDCl3) δ: 168.9, 168.2, 168.0, 138.1, 135.5, 135.5, 135.5, 134.3, 128.6, 128.6, 128.5, 128.4, 128.4, 128.3, 125.1, 117.6, 67.2, 67.1, 67.1, 63.1, 63.1, 57.1, 52.4, 44.3, 32.9, 32.8, 32.5, 32.3, 32.0, 29.3, 29.3, 29.2, 29.1, 27.0, 25.8, 25.7. HRMS (ESI-TOF) calcd for C27H34O5Na [M＋Na]＋ 461.2304, found 461.2308. HPLC analysis: chiral MD (2) (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=90∶10, 1.0 mL/min, 25 ℃, 210 nm), tR(minor)=20.29 min, tR(major)=21.57 min.
＋30.35 (c 0.3, acetone); 1H NMR (500 MHz, CDCl3) δ: 7.35~7.27 (m, 14H), 5.67~5.57 (m, 1H), 5.52~5.45 (m, 0.42H), 5.37~5.30 (m, 0.45H), 5.14 (dd, J=3.1, 1.5 Hz, 3H), 5.10 (s, 2H), 5.05~5.01 (m, 1H), 5.00 (s, 1H), 3.62 (td, J=6.6, 2.6 Hz, 2.82H), 3.50 (t, J=7.6 Hz, 0.42H), 3.46 (d, J=8.8 Hz, 1H), 2.78 (q, J=9.3 Hz, 1H), 2.62 (t, J=7.2 Hz, 0.80H), 1.91 (q, J=6.7 Hz, 0.87H), 1.58~1.51 (m, 4H), 1.35~1.21 (m, 12H); 13C NMR (126 MHz, CDCl3) δ: 168.9, 168.2, 168.0, 138.1, 135.5, 135.5, 135.5, 134.3, 128.6, 128.6, 128.5, 128.4, 128.4, 128.3, 125.1, 117.6, 67.2, 67.1, 67.1, 63.1, 63.1, 57.1, 52.4, 44.3, 32.9, 32.8, 32.5, 32.3, 32.0, 29.3, 29.3, 29.2, 29.1, 27.0, 25.8, 25.7. HRMS (ESI-TOF) calcd for C27H34O5Na [M＋Na]＋ 461.2304, found 461.2308. HPLC analysis: chiral MD (2) (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=90∶10, 1.0 mL/min, 25 ℃, 210 nm), tR(minor)=20.29 min, tR(major)=21.57 min.Dibenzyl (R)-2-(7-(benzoyloxy)hept-1-en-3-yl)malonate (3o) and dibenzyl (E)-2-(7-(benzoyloxy)hept-2-en-1-yl)-malonate (3o'): Yellow oil (31.7 mg, 65% yield, B∶L=2.5∶1, 89% ee). Eluent: V(petroleum ether)∶V(ethyl acetate)=90∶10. 
＋30.35 (c 0.3, acetone); 1H NMR (500 MHz, CDCl3) δ: 8.09~8.02 (m, 2.84H), 7.58~7.52 (m, 1.43H), 7.47~7.41 (m, 2.94H), 7.34~7.29 (m, 14H), 5.68~5.57 (m, 1H), 5.52~5.45 (m, 0.44H), 5.37~5.31 (m, 0.43H), 5.15 (dd, J=3.6, 1.7 Hz, 3H), 5.10 (s, 2H), 5.05~4.97 (m, 2H), 4.31 (td, J=6.7, 3.2 Hz, 2.83H), 3.50 (t, J=7.6 Hz, 0.39H), 3.47 (d, J=8.8 Hz, 1H), 2.79 (q, J=9.3 Hz, 1H), 2.65~2.60 (m, 0.80H), 1.92 (q, J=6.7 Hz, 0.85H), 1.78~1.71 (m, 2.80H), 1.45~1.39 (m, 2.97H), 1.24~1.15 (m, 2.33H); 13C NMR (126 MHz, CDCl3) δ: 168.8, 168.2, 168.0, 166.8, 165.2, 138.0, 135.5, 135.5, 135.5, 134.2, 132.9, 130.6, 129.6, 128.8, 128.8, 128.6, 128.6, 128.5, 128.4, 128.4, 128.3, 125.1, 117.7, 68.1, 67.2, 67.1, 67.1, 65.2, 57.1, 52.4, 44.3, 32.3, 29.3, 29.3, 29.2, 29.2, 29.1, 28.8, 28.8, 27.0, 26.1, 26.1. HRMS (ESI-TOF) calcd for C31H32O6Na [M＋Na]＋ 523.2097, found 523.2099. HPLC analysis: chiral IC (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=98∶2, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=27.81 min, tR(major)=30.70 min.
＋30.35 (c 0.3, acetone); 1H NMR (500 MHz, CDCl3) δ: 8.09~8.02 (m, 2.84H), 7.58~7.52 (m, 1.43H), 7.47~7.41 (m, 2.94H), 7.34~7.29 (m, 14H), 5.68~5.57 (m, 1H), 5.52~5.45 (m, 0.44H), 5.37~5.31 (m, 0.43H), 5.15 (dd, J=3.6, 1.7 Hz, 3H), 5.10 (s, 2H), 5.05~4.97 (m, 2H), 4.31 (td, J=6.7, 3.2 Hz, 2.83H), 3.50 (t, J=7.6 Hz, 0.39H), 3.47 (d, J=8.8 Hz, 1H), 2.79 (q, J=9.3 Hz, 1H), 2.65~2.60 (m, 0.80H), 1.92 (q, J=6.7 Hz, 0.85H), 1.78~1.71 (m, 2.80H), 1.45~1.39 (m, 2.97H), 1.24~1.15 (m, 2.33H); 13C NMR (126 MHz, CDCl3) δ: 168.8, 168.2, 168.0, 166.8, 165.2, 138.0, 135.5, 135.5, 135.5, 134.2, 132.9, 130.6, 129.6, 128.8, 128.8, 128.6, 128.6, 128.5, 128.4, 128.4, 128.3, 125.1, 117.7, 68.1, 67.2, 67.1, 67.1, 65.2, 57.1, 52.4, 44.3, 32.3, 29.3, 29.3, 29.2, 29.2, 29.1, 28.8, 28.8, 27.0, 26.1, 26.1. HRMS (ESI-TOF) calcd for C31H32O6Na [M＋Na]＋ 523.2097, found 523.2099. HPLC analysis: chiral IC (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=98∶2, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=27.81 min, tR(major)=30.70 min.Dibenzyl (R)-2-(6-acetoxyhex-1-en-3-yl)malonate (3p) and dibenzyl (E)-2-(6-acetoxyhex-2-en-1-yl)malonate (3p'): Yellow oil (30.5 mg, 72% yield, B∶L=2.5∶1, 87% ee). Eluent: V(petroleum ether)∶V(ethyl acetate)=90∶10. 
－27.06 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.34~7.27 (m, 14H), 5.68~5.55 (m, 1H), 5.51~5.43 (m, 0.46H), 5.38 (dd, J=14.5, 7.5 Hz, 0.56H), 5.14 (s, 3.44H), 5.10 (s, 2H), 5.04 (dd, J=13.8, 2.4 Hz, 2H), 4.05~3.91 (m, 2.87H), 3.48 (dd, J=14.4, 8.0 Hz, 1.39H), 2.79 (td, J=9.0, 6.2 Hz, 1H), 2.62 (t, J=7.1 Hz, 0.86H), 2.02 (d, J=11.3 Hz, 5.34H), 1.60 (s, 1H), 1.50 (td, J=11.9, 4.1 Hz, 2H), 1.37~1.29 (m, 1H); 13C NMR (101 MHz, CDCl3) δ: 171.22, 168.78, 168.01, 167.85, 137.43, 135.52, 135.42, 132.74, 128.75, 128.69, 128.67, 128.64, 128.54, 128.47, 128.44, 128.32, 126.22, 118.34, 67.28, 67.21, 67.18, 64.25, 57.01, 44.04, 28.70, 28.22, 26.37, 21.08. HRMS (ESI-TOF) calcd for C25H27O6 [M－H]＋ 423.1713, found 423.1714. HPLC analysis: chiral IG-3 (250 mm×4.6 mm, 3 µm, V(hexane)∶V(i-PrOH)=95∶5, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=46.70 min, tR(major)=54.66 min.
－27.06 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.34~7.27 (m, 14H), 5.68~5.55 (m, 1H), 5.51~5.43 (m, 0.46H), 5.38 (dd, J=14.5, 7.5 Hz, 0.56H), 5.14 (s, 3.44H), 5.10 (s, 2H), 5.04 (dd, J=13.8, 2.4 Hz, 2H), 4.05~3.91 (m, 2.87H), 3.48 (dd, J=14.4, 8.0 Hz, 1.39H), 2.79 (td, J=9.0, 6.2 Hz, 1H), 2.62 (t, J=7.1 Hz, 0.86H), 2.02 (d, J=11.3 Hz, 5.34H), 1.60 (s, 1H), 1.50 (td, J=11.9, 4.1 Hz, 2H), 1.37~1.29 (m, 1H); 13C NMR (101 MHz, CDCl3) δ: 171.22, 168.78, 168.01, 167.85, 137.43, 135.52, 135.42, 132.74, 128.75, 128.69, 128.67, 128.64, 128.54, 128.47, 128.44, 128.32, 126.22, 118.34, 67.28, 67.21, 67.18, 64.25, 57.01, 44.04, 28.70, 28.22, 26.37, 21.08. HRMS (ESI-TOF) calcd for C25H27O6 [M－H]＋ 423.1713, found 423.1714. HPLC analysis: chiral IG-3 (250 mm×4.6 mm, 3 µm, V(hexane)∶V(i-PrOH)=95∶5, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=46.70 min, tR(major)=54.66 min.Dibenzyl (R)-2-(7-phenoxyhept-1-en-3-yl)malonate (3q) and dibenzyl (E)-2-(7-phenoxyhept-2-en-1-yl)malonate (3q'): Yellow oil (19.2 mg, 56% yield, B∶L=2.5∶1, 75% ee). Eluent: V(petroleum ether)∶V(ethyl acetate)=90∶10. 
＋47.68 (c 0.3, acetone); 1H NMR (500 MHz, CDCl3) δ: 7.38~7.24 (m, 18H), 6.95~6.90 (m, 1H), 6.90~6.84 (m, 2H), 5.68~5.58 (m, 1H), 5.53~5.46 (m, 0.42H), 5.40~5.33 (m, 0.45H), 5.14 (d, J=1.3 Hz, 3H), 5.10 (s, 2H), 5.06~5.00 (m, 2H), 3.90 (dt, J=17.4, 6.4 Hz, 2.80H), 3.48 (q, J=8.4 Hz, 1.40H), 2.85~2.76 (m, 1H), 2.65~2.59 (m, 0.76H), 1.99 (q, J=7.1 Hz, 0.80H), 1.77~1.62 (m, 3H), 1.53~1.42 (m, 3H), 1.37~1.30 (m, 2H); 13C NMR (101 MHz, CDCl3) δ: 168.9, 168.2, 168.0, 159.1, 137.8, 135.5, 135.5, 133.8, 129.5, 129.5, 128.8, 128.7, 128.6, 128.6, 128.5, 128.5, 128.5, 128.3, 125.7, 120.6, 118.0, 114.6, 114.6, 67.7, 67.6, 67.2, 67.2, 67.1, 57.1, 52.4, 44.3, 32.2, 32.1, 29.1, 28.8, 25.8, 23.7. HRMS (ESI-TOF) calcd for C30H33O5 [M＋H]＋ 473.2328, found 473.2325. HPLC analysis: chiral MX (2) (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=98∶2, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=33.32 min, tR(major)=43.37 min.
＋47.68 (c 0.3, acetone); 1H NMR (500 MHz, CDCl3) δ: 7.38~7.24 (m, 18H), 6.95~6.90 (m, 1H), 6.90~6.84 (m, 2H), 5.68~5.58 (m, 1H), 5.53~5.46 (m, 0.42H), 5.40~5.33 (m, 0.45H), 5.14 (d, J=1.3 Hz, 3H), 5.10 (s, 2H), 5.06~5.00 (m, 2H), 3.90 (dt, J=17.4, 6.4 Hz, 2.80H), 3.48 (q, J=8.4 Hz, 1.40H), 2.85~2.76 (m, 1H), 2.65~2.59 (m, 0.76H), 1.99 (q, J=7.1 Hz, 0.80H), 1.77~1.62 (m, 3H), 1.53~1.42 (m, 3H), 1.37~1.30 (m, 2H); 13C NMR (101 MHz, CDCl3) δ: 168.9, 168.2, 168.0, 159.1, 137.8, 135.5, 135.5, 133.8, 129.5, 129.5, 128.8, 128.7, 128.6, 128.6, 128.5, 128.5, 128.5, 128.3, 125.7, 120.6, 118.0, 114.6, 114.6, 67.7, 67.6, 67.2, 67.2, 67.1, 57.1, 52.4, 44.3, 32.2, 32.1, 29.1, 28.8, 25.8, 23.7. HRMS (ESI-TOF) calcd for C30H33O5 [M＋H]＋ 473.2328, found 473.2325. HPLC analysis: chiral MX (2) (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=98∶2, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=33.32 min, tR(major)=43.37 min.Dibenzyl (R)-2-(6-((thiophene-2-carbonyl)oxy)hex-1-en-3-yl)malonate (3r) and dibenzyl (Z)-2-(6-((thiophene-2-carbonyl)oxy)hex-2-en-1-yl)malonate (3r'): Yellow oil (14.7 mg, 38% yield, B∶L=2∶1, 75% ee). Eluent: V(petroleum ether)∶V(ethyl acetate)=90∶10. 
＋30.35 (c 0.3, acetone); 1H NMR (500 MHz, CDCl3) δ: 7.80 (dd, J=3.7, 1.3 Hz, 0.54H), 7.78 (dd, J=3.7, 1.3 Hz, 2H), 7.55~7.53 (m, 0.55H), 7.53~7.51 (m, 2H), 7.33~7.28 (m, 15H), 7.15~7.03 (m, 2H), 5.71~5.60 (m, 1H), 5.54~5.48 (m, 0.51H), 5.44~5.36 (m, 0.53H), 5.17~5.11 (m, 6H), 5.11~5.03 (m, 2H), 4.28~4.15 (m, 3H), 3.52 (t, J=8.9 Hz, 0.46H), 3.50 (d, J=8.9 Hz, 1H), 2.90~2.82 (m, 1H), 2.67~2.60 (m, 1H), 2.22 (s, 1H), 2.11~2.03 (m, 1H), 1.83~1.70 (m, 3H), 1.66~1.55 (m, 2H), 1.48~1.40 (m, 1H); 13C NMR (126 MHz, CDCl3) δ: 168.7, 167.9, 167.8, 164.3, 162.3, 162.3, 137.4, 133.4, 132.4, 128.7, 128.7, 128.6, 128.6, 128.6, 128.5, 128.4, 128.4, 128.4, 128.3, 127.8, 127.0, 118.3, 68.2, 67.2, 67.1, 67.1, 64.8, 57.0, 44.0, 28.7, 26.4. HRMS (ESI-TOF) calcd for C28H29O6S [M＋H]＋ 493.1685, found 493.1680. HPLC analysis: chiral IC (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=90∶10, 1.0 mL/min, 25 ℃, 210 nm), tR(minor)=33.32 min, tR(major)=24.32 min.
＋30.35 (c 0.3, acetone); 1H NMR (500 MHz, CDCl3) δ: 7.80 (dd, J=3.7, 1.3 Hz, 0.54H), 7.78 (dd, J=3.7, 1.3 Hz, 2H), 7.55~7.53 (m, 0.55H), 7.53~7.51 (m, 2H), 7.33~7.28 (m, 15H), 7.15~7.03 (m, 2H), 5.71~5.60 (m, 1H), 5.54~5.48 (m, 0.51H), 5.44~5.36 (m, 0.53H), 5.17~5.11 (m, 6H), 5.11~5.03 (m, 2H), 4.28~4.15 (m, 3H), 3.52 (t, J=8.9 Hz, 0.46H), 3.50 (d, J=8.9 Hz, 1H), 2.90~2.82 (m, 1H), 2.67~2.60 (m, 1H), 2.22 (s, 1H), 2.11~2.03 (m, 1H), 1.83~1.70 (m, 3H), 1.66~1.55 (m, 2H), 1.48~1.40 (m, 1H); 13C NMR (126 MHz, CDCl3) δ: 168.7, 167.9, 167.8, 164.3, 162.3, 162.3, 137.4, 133.4, 132.4, 128.7, 128.7, 128.6, 128.6, 128.6, 128.5, 128.4, 128.4, 128.4, 128.3, 127.8, 127.0, 118.3, 68.2, 67.2, 67.1, 67.1, 64.8, 57.0, 44.0, 28.7, 26.4. HRMS (ESI-TOF) calcd for C28H29O6S [M＋H]＋ 493.1685, found 493.1680. HPLC analysis: chiral IC (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=90∶10, 1.0 mL/min, 25 ℃, 210 nm), tR(minor)=33.32 min, tR(major)=24.32 min.Dibenzyl (R)-2-(10-(tosyloxy)dec-1-en-3-yl)malonate (3s) and dibenzyl (E)-2-(10-(tosyloxy)dec-2-en-1-yl)-malonate (3s'): Yellow oil (37.1 mg, 66% yield, B∶L=2∶1, 80% ee). Eluent: V(petroleum ether)∶V(ethyl acetate)=90∶10. 
＋3.71 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.78 (d, J=8.3 Hz, 3H), 7.53~7.15 (m, 17H), 5.60 (dt, J=17.5, 9.5 Hz, 1H), 5.45 (dt, J=13.9, 6.6 Hz, 1H), 5.36~5.27 (m, 1H), 5.14 (d, J=1.5 Hz, 3H), 5.09 (s, 2H), 5.05~4.99 (m, 1H), 4.98 (d, J=2.0 Hz, 1H), 4.00 (td, J=6.5, 2.9 Hz, 3H), 3.50 (d, J=7.6 Hz, 1H), 3.44 (d, J=8.8 Hz, 1H), 2.75 (q, J=9.3 Hz, 1H), 2.61 (t, J=7.2 Hz, 1H), 2.44 (s, 4H), 1.88 (q, J=6.8 Hz, 1H), 1.62 (d, J=7.0 Hz, 1H), 1.57 (d, J=6.6 Hz, 2H), 1.33~1.05 (m, 14H); 13C NMR (101 MHz, CDCl3) δ: 168.9, 168.2, 168.0, 144.8, 138.0, 135.5, 129.9, 128.7, 128.6, 128.5, 128.5, 128.4, 128.3, 128.0, 117.7, 70.8, 67.2, 67.1, 57.1, 44.3, 32.4, 32.3, 29.2, 28.9, 28.9, 26.9, 25.4, 21.8. HRMS (ESI-TOF) calcd for C34H41O7S [M＋H]＋ 593.2573, found 593.2579. HPLC analysis: chiral MX (2) (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=90∶10, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=64.95 min, tR(major)=68.88 min.
＋3.71 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.78 (d, J=8.3 Hz, 3H), 7.53~7.15 (m, 17H), 5.60 (dt, J=17.5, 9.5 Hz, 1H), 5.45 (dt, J=13.9, 6.6 Hz, 1H), 5.36~5.27 (m, 1H), 5.14 (d, J=1.5 Hz, 3H), 5.09 (s, 2H), 5.05~4.99 (m, 1H), 4.98 (d, J=2.0 Hz, 1H), 4.00 (td, J=6.5, 2.9 Hz, 3H), 3.50 (d, J=7.6 Hz, 1H), 3.44 (d, J=8.8 Hz, 1H), 2.75 (q, J=9.3 Hz, 1H), 2.61 (t, J=7.2 Hz, 1H), 2.44 (s, 4H), 1.88 (q, J=6.8 Hz, 1H), 1.62 (d, J=7.0 Hz, 1H), 1.57 (d, J=6.6 Hz, 2H), 1.33~1.05 (m, 14H); 13C NMR (101 MHz, CDCl3) δ: 168.9, 168.2, 168.0, 144.8, 138.0, 135.5, 129.9, 128.7, 128.6, 128.5, 128.5, 128.4, 128.3, 128.0, 117.7, 70.8, 67.2, 67.1, 57.1, 44.3, 32.4, 32.3, 29.2, 28.9, 28.9, 26.9, 25.4, 21.8. HRMS (ESI-TOF) calcd for C34H41O7S [M＋H]＋ 593.2573, found 593.2579. HPLC analysis: chiral MX (2) (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=90∶10, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=64.95 min, tR(major)=68.88 min.Dibenzyl (R)-2-(7-((N,4-dimethylphenyl)sulfonamido)-hept-1-en-3-yl)malonate (3t) and dibenzyl (E)-2-(7-((N,4-dimethylphenyl)sulfonamido)hept-2-en-1-yl)malonate (3t'): Yellow oil (39.1 mg, 70% yield, B∶L=5∶1, 55% ee). Eluent: V(petroleum ether)∶V(ethyl acetate)=90∶10. 
41.27 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.69~7.62 (m, 3H), 7.34~7.28 (m, 16H), 5.67~5.52 (m, 1H), 5.47~5.42 (m, 0.49H), 5.37~5.32 (m, 0.50H), 5.19~5.06 (m, 5H), 5.01 (q, J=13.9 Hz, 2H), 3.47 (d, J=8.2 Hz, 0.41H), 3.45 (d, J=8.8 Hz, 1H), 2.97~2.88 (m, 3H), 2.76 (dd, J=9.2, 3.4 Hz, 1H), 2.66 (d, J=8.2 Hz, 4H), 2.64~2.57 (m, 1H), 2.42 (d, J=2.5 Hz, 5H), 2.11~2.00 (m, 1H), 1.93 (q, J=7.1 Hz, 1H), 1.56~1.25 (m, 9H); 13C NMR (101 MHz, CDCl3) δ: 168.13, 167.96, 143.31, 137.72, 135.47, 134.71, 129.74, 128.68, 128.63, 128.50, 128.48, 128.47, 128.30, 127.55, 118.03, 67.24, 67.14, 57.05, 49.95, 44.15, 34.68, 31.79, 27.33, 24.01, 21.62. HRMS (ESI-TOF) calcd for C32H36NO6S [M－H]＋ 564.2268, found 562.2266. HPLC analysis: chiral MX (2) (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=80∶20, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=37.43 min, tR(major)=41.27 min.
41.27 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.69~7.62 (m, 3H), 7.34~7.28 (m, 16H), 5.67~5.52 (m, 1H), 5.47~5.42 (m, 0.49H), 5.37~5.32 (m, 0.50H), 5.19~5.06 (m, 5H), 5.01 (q, J=13.9 Hz, 2H), 3.47 (d, J=8.2 Hz, 0.41H), 3.45 (d, J=8.8 Hz, 1H), 2.97~2.88 (m, 3H), 2.76 (dd, J=9.2, 3.4 Hz, 1H), 2.66 (d, J=8.2 Hz, 4H), 2.64~2.57 (m, 1H), 2.42 (d, J=2.5 Hz, 5H), 2.11~2.00 (m, 1H), 1.93 (q, J=7.1 Hz, 1H), 1.56~1.25 (m, 9H); 13C NMR (101 MHz, CDCl3) δ: 168.13, 167.96, 143.31, 137.72, 135.47, 134.71, 129.74, 128.68, 128.63, 128.50, 128.48, 128.47, 128.30, 127.55, 118.03, 67.24, 67.14, 57.05, 49.95, 44.15, 34.68, 31.79, 27.33, 24.01, 21.62. HRMS (ESI-TOF) calcd for C32H36NO6S [M－H]＋ 564.2268, found 562.2266. HPLC analysis: chiral MX (2) (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=80∶20, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=37.43 min, tR(major)=41.27 min.Diphenyl (R)-2-(oct-1-en-3-yl)malonate (3u) and diphenyl (E)-2-(oct-2-en-1-yl)malonate (3u'): Yellow oil (25.2 mg, 69% yield, B∶L=4∶1, 67% ee). Eluent: V(petroleum ether)∶V(ethyl acetate)=90∶10. 
＋3.28 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.45~7.34 (m, 5H), 7.29~7.21 (m, 3H), 7.17~7.08 (m, 5H), 5.88 (dt, J=17.1, 9.8 Hz, 1H), 5.75~5.67 (m, 0.27H), 5.60~5.51 (m, 0.22H), 5.31~5.21 (m, 2H), 3.88 (t, J=7.6 Hz, 0.25H), 3.85 (d, J=8.2 Hz, 1H), 3.02 (q, J=9.6 Hz, 1H), 2.88~2.82 (m, 0.47H), 2.05 (q, J=7.0 Hz, 0.56H), 1.75~1.66 (m, 1H), 1.59~1.50 (m, 1H), 1.43~1.27 (m, 7H), 0.93~0.86 (m, 4H); 13C NMR (101 MHz, CDCl3) δ: 167.44, 166.88, 166.63, 150.62, 150.58, 137.91, 135.09, 129.69, 129.67, 129.63, 126.37, 126.36, 126.32, 124.69, 121.50, 121.46, 118.31, 56.81, 52.41, 44.48, 32.65, 32.60, 32.08, 31.66, 31.47, 29.12, 26.84, 22.66, 14.15. HRMS (ESI-TOF) calcd for C23H27O4 [M＋H]＋ 367.1909, found 367.1904. HPLC analysis: chiral MD (2) (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=98∶2, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=33.32 min, tR(major)=35.16 min.
＋3.28 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.45~7.34 (m, 5H), 7.29~7.21 (m, 3H), 7.17~7.08 (m, 5H), 5.88 (dt, J=17.1, 9.8 Hz, 1H), 5.75~5.67 (m, 0.27H), 5.60~5.51 (m, 0.22H), 5.31~5.21 (m, 2H), 3.88 (t, J=7.6 Hz, 0.25H), 3.85 (d, J=8.2 Hz, 1H), 3.02 (q, J=9.6 Hz, 1H), 2.88~2.82 (m, 0.47H), 2.05 (q, J=7.0 Hz, 0.56H), 1.75~1.66 (m, 1H), 1.59~1.50 (m, 1H), 1.43~1.27 (m, 7H), 0.93~0.86 (m, 4H); 13C NMR (101 MHz, CDCl3) δ: 167.44, 166.88, 166.63, 150.62, 150.58, 137.91, 135.09, 129.69, 129.67, 129.63, 126.37, 126.36, 126.32, 124.69, 121.50, 121.46, 118.31, 56.81, 52.41, 44.48, 32.65, 32.60, 32.08, 31.66, 31.47, 29.12, 26.84, 22.66, 14.15. HRMS (ESI-TOF) calcd for C23H27O4 [M＋H]＋ 367.1909, found 367.1904. HPLC analysis: chiral MD (2) (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=98∶2, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=33.32 min, tR(major)=35.16 min.Diethyl (R)-2-(oct-1-en-3-yl)malonate (3v) and diethyl (E)-2-(oct-2-en-1-yl)malonate (3v'): Yellow oil (13.2 mg, 48% yield, B∶L=2.5∶1, 82% ee). Eluent: V(petroleum ether)∶V(ethyl acetate)=90∶10. 
＋3.28 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 5.68~5.57 (m, 1H), 5.55~5.47 (m, 0.44H), 5.38~5.29 (m, 0.40H), 5.10~5.02 (m, 2H), 4.21~4.10 (m, 5.64H), 3.39~3.27 (m, 1.36H), 2.74 (q, J=9.3 Hz, 1H), 2.59~2.53 (m, 0.89H), 1.98~1.90 (m, 0.80H), 1.47~1.39 (m, 1H), 1.25 (d, J=6.6 Hz, 16H), 0.85 (td, J=6.9, 2.7 Hz, 4H); 13C NMR (101 MHz, CDCl3) δ: 169.20, 168.56, 168.37, 138.34, 134.12, 125.31, 117.37, 61.39, 61.24, 57.17, 52.44, 44.22, 32.54, 32.37, 31.99, 31.65, 31.39, 29.09, 26.73, 22.61, 14.22, 14.12. HRMS (ESI-TOF) calcd for C15H27O4 [M＋H]＋ 271.1909, found 271.1905. HPLC analysis: chiral IG-3 (250 mm×4.6 mm, 3 µm, V(hexane)∶V(i-PrOH)=98∶2, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=21.50 min, tR(major)=25.15 min.
＋3.28 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 5.68~5.57 (m, 1H), 5.55~5.47 (m, 0.44H), 5.38~5.29 (m, 0.40H), 5.10~5.02 (m, 2H), 4.21~4.10 (m, 5.64H), 3.39~3.27 (m, 1.36H), 2.74 (q, J=9.3 Hz, 1H), 2.59~2.53 (m, 0.89H), 1.98~1.90 (m, 0.80H), 1.47~1.39 (m, 1H), 1.25 (d, J=6.6 Hz, 16H), 0.85 (td, J=6.9, 2.7 Hz, 4H); 13C NMR (101 MHz, CDCl3) δ: 169.20, 168.56, 168.37, 138.34, 134.12, 125.31, 117.37, 61.39, 61.24, 57.17, 52.44, 44.22, 32.54, 32.37, 31.99, 31.65, 31.39, 29.09, 26.73, 22.61, 14.22, 14.12. HRMS (ESI-TOF) calcd for C15H27O4 [M＋H]＋ 271.1909, found 271.1905. HPLC analysis: chiral IG-3 (250 mm×4.6 mm, 3 µm, V(hexane)∶V(i-PrOH)=98∶2, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=21.50 min, tR(major)=25.15 min.Bis(4-chlorobenzyl) (R)-2-(oct-1-en-3-yl)malonate (3w) and bis(4-chlorobenzyl) (E)-2-(oct-2-en-1-yl)malonate (3w'): Yellow oil (35.2 mg, 77% yield, B∶L=3.3∶1, 71% ee). Eluent: V(petroleum ether)∶V(ethyl acetate)=90∶10. 
＋9.59 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.33~7.27 (m, 5H), 7.22 (dd, J=8.6, 6.8 Hz, 5H), 5.66~5.54 (m, 1H), 5.52~5.43 (m, 0.31H), 5.35~5.27 (m, 0.33H), 5.14~5.07 (m, 3H), 5.05 (s, 2H), 5.04~4.97 (m, 2H), 3.48 (t, J=7.6 Hz, 0.30H), 3.44 (d, J=8.8 Hz, 1H), 2.76 (q, J=9.2 Hz, 1H), 2.63~2.55 (m, 0.60H), 1.90 (q, J=6.8 Hz, 0.63H), 1.36~1.12 (m, 10H), 0.86 (dt, J=9.2, 6.9 Hz, 4H); 13C NMR (101 MHz, CDCl3) δ: 168.66, 168.03, 167.85, 137.95, 134.58, 134.48, 134.40, 133.95, 133.92, 129.87, 129.70, 128.86, 128.80, 124.79, 117.70, 66.32, 66.30, 66.21, 57.01, 52.32, 44.34, 32.50, 32.32, 31.96, 31.61, 31.41, 29.01, 26.69, 22.60, 22.58, 14.17, 14.12. HRMS (ESI-TOF) calcd for C25H29Cl2O4 [M＋H]＋ 463.1443, found 463.1440. HPLC analysis: chiral MD (2) (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=98∶2, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=19.88 min, tR(major)=21.78 min.
＋9.59 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.33~7.27 (m, 5H), 7.22 (dd, J=8.6, 6.8 Hz, 5H), 5.66~5.54 (m, 1H), 5.52~5.43 (m, 0.31H), 5.35~5.27 (m, 0.33H), 5.14~5.07 (m, 3H), 5.05 (s, 2H), 5.04~4.97 (m, 2H), 3.48 (t, J=7.6 Hz, 0.30H), 3.44 (d, J=8.8 Hz, 1H), 2.76 (q, J=9.2 Hz, 1H), 2.63~2.55 (m, 0.60H), 1.90 (q, J=6.8 Hz, 0.63H), 1.36~1.12 (m, 10H), 0.86 (dt, J=9.2, 6.9 Hz, 4H); 13C NMR (101 MHz, CDCl3) δ: 168.66, 168.03, 167.85, 137.95, 134.58, 134.48, 134.40, 133.95, 133.92, 129.87, 129.70, 128.86, 128.80, 124.79, 117.70, 66.32, 66.30, 66.21, 57.01, 52.32, 44.34, 32.50, 32.32, 31.96, 31.61, 31.41, 29.01, 26.69, 22.60, 22.58, 14.17, 14.12. HRMS (ESI-TOF) calcd for C25H29Cl2O4 [M＋H]＋ 463.1443, found 463.1440. HPLC analysis: chiral MD (2) (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=98∶2, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=19.88 min, tR(major)=21.78 min.Bis(4-bromobenzyl) (R)-2-(oct-1-en-3-yl)malonate (3x) and bis(4-bromobenzyl) (E)-2-(oct-2-en-1-yl)malonate (3x'): Yellow oil (20.8 mg, 56% yield, B∶L=3.3∶1, 73% ee). Eluent: V(petroleum ether)∶V(ethyl acetate)=90∶10. 
－10.88 (c 0.3, acetone); 1H NMR (500 MHz, CDCl3) δ: 7.48~7.43 (m, 5H), 7.15 (t, J=8.5 Hz, 5H), 5.60 (dt, J=17.5, 9.5 Hz, 1H), 5.50~5.44 (m, 0.36H), 5.33~5.28 (m, 0.37H), 5.12~5.06 (m, 3H), 5.03 (s, 2H), 5.03~4.98 (m, 2H), 3.48 (d, J=7.6 Hz, 0.30H), 3.44 (d, J=8.8 Hz, 1H), 2.75 (q, J=9.3 Hz, 1H), 2.62~2.57 (m, 0.65H), 1.90 (q, J=6.9 Hz, 0.68H), 1.40~1.16 (m, 10H), 0.86 (dt, J=11.0, 7.0 Hz, 4H); 13C NMR (126 MHz, CDCl3) δ: 168.65, 168.02, 167.84, 137.96, 134.61, 134.46, 134.43, 131.84, 131.79, 130.16, 129.99, 124.78, 122.65, 122.59, 122.57, 117.73, 66.37, 66.34, 66.25, 57.02, 52.32, 44.35, 32.52, 32.34, 31.97, 31.62, 31.43, 29.03, 26.71, 22.63, 22.60, 14.19, 14.15. HRMS (ESI-TOF) calcd for C25H29Br2O4 [M＋H]＋ 551.0433, found 551.0430. HPLC analysis: chiral MD (2) (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=95∶5, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=50.71 min, tR(major)=53.21 min.
－10.88 (c 0.3, acetone); 1H NMR (500 MHz, CDCl3) δ: 7.48~7.43 (m, 5H), 7.15 (t, J=8.5 Hz, 5H), 5.60 (dt, J=17.5, 9.5 Hz, 1H), 5.50~5.44 (m, 0.36H), 5.33~5.28 (m, 0.37H), 5.12~5.06 (m, 3H), 5.03 (s, 2H), 5.03~4.98 (m, 2H), 3.48 (d, J=7.6 Hz, 0.30H), 3.44 (d, J=8.8 Hz, 1H), 2.75 (q, J=9.3 Hz, 1H), 2.62~2.57 (m, 0.65H), 1.90 (q, J=6.9 Hz, 0.68H), 1.40~1.16 (m, 10H), 0.86 (dt, J=11.0, 7.0 Hz, 4H); 13C NMR (126 MHz, CDCl3) δ: 168.65, 168.02, 167.84, 137.96, 134.61, 134.46, 134.43, 131.84, 131.79, 130.16, 129.99, 124.78, 122.65, 122.59, 122.57, 117.73, 66.37, 66.34, 66.25, 57.02, 52.32, 44.35, 32.52, 32.34, 31.97, 31.62, 31.43, 29.03, 26.71, 22.63, 22.60, 14.19, 14.15. HRMS (ESI-TOF) calcd for C25H29Br2O4 [M＋H]＋ 551.0433, found 551.0430. HPLC analysis: chiral MD (2) (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=95∶5, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=50.71 min, tR(major)=53.21 min.Bis(4-methylbenzyl) (R)-2-(oct-1-en-3-yl)malonate (3y) and bis(4-methylbenzyl) (E)-2-(oct-2-en-1-yl)malonate (3y'): Yellow oil (26.5 mg, 63% yield, B∶L=2.5∶1, 77% ee). Eluent: V(petroleum ether)∶V(ethyl acetate)=90∶10. 
－17.22 (c 0.3, acetone); 1H NMR (500 MHz, CDCl3) δ: 7.23~7.17 (m, 5.66H), 7.14 (d, J=7.6 Hz, 5.68H), 5.68~5.57 (m, 1H), 5.52~5.45 (m, 0.41H), 5.36~5.29 (m, 0.45H), 5.13~5.10 (m, 3H), 5.06 (s, 2H), 5.05~4.98 (m, 2H), 3.50~3.42 (m, 1.31H), 2.82~2.74 (m, 1H), 2.61 (t, J=7.2 Hz, 0.73H), 2.36 (s, 8.54H), 1.91 (q, J=5.5 Hz, 0.86H), 1.42~1.36 (m, 1H), 1.30~1.15 (m, 9H), 0.86 (q, J=7.9 Hz, 4H); 13C NMR (101 MHz, CDCl3). HRMS (ESI-TOF) calcd for C27H35O4 [M＋H]＋ 423.2535, found 423.2538. HPLC analysis: chiral IC (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=99∶1, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=20.54 min, tR(major)=21.56 min.
－17.22 (c 0.3, acetone); 1H NMR (500 MHz, CDCl3) δ: 7.23~7.17 (m, 5.66H), 7.14 (d, J=7.6 Hz, 5.68H), 5.68~5.57 (m, 1H), 5.52~5.45 (m, 0.41H), 5.36~5.29 (m, 0.45H), 5.13~5.10 (m, 3H), 5.06 (s, 2H), 5.05~4.98 (m, 2H), 3.50~3.42 (m, 1.31H), 2.82~2.74 (m, 1H), 2.61 (t, J=7.2 Hz, 0.73H), 2.36 (s, 8.54H), 1.91 (q, J=5.5 Hz, 0.86H), 1.42~1.36 (m, 1H), 1.30~1.15 (m, 9H), 0.86 (q, J=7.9 Hz, 4H); 13C NMR (101 MHz, CDCl3). HRMS (ESI-TOF) calcd for C27H35O4 [M＋H]＋ 423.2535, found 423.2538. HPLC analysis: chiral IC (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=99∶1, 0.5 mL/min, 25 ℃, 210 nm), tR(minor)=20.54 min, tR(major)=21.56 min.4.3 Synthesis of 4
To a solution of 3a (0.2 mmol) in tetrahydrofuran (THF) (0.4 mL), NaH (1.5 equiv.) was added portion wise at 0 ℃. This solution was allowed to stir for 30 min and allyl bromide (1.5 equiv.) was added to the solution slowly. Followed by the stirring of the reaction mixture at room temperature for next 12 h. The progress of the reaction was monitored by the TLC analysis. After completion of the reaction, the mixture was filtered through the celite and washed with ethyl acetate (10 mL×2). The organic layer was extracted with ethyl acetate, concentrated under reduced pressure and subjected to column chromatographic purification, resulting into 4[10] as a yellow oil (32.5 mg, 75% yield, 87% ee). Eluent: V(petroleum ether)∶V(ethyl acetate)=90∶10. 
－24.52 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.37~7.26 (m, 10H), 5.82~5.68 (m, 1H), 5.51 (dt, J=17.0, 10.1 Hz, 1H), 5.20~5.10 (m, 4H), 5.10~5.06 (m, 1H), 5.06~4.94 (m, 3H), 2.66 (d, J=7.3 Hz, 2H), 2.59 (td, J=10.2, 2.3 Hz, 1H), 1.60 (dt, J=10.4, 3.9 Hz, 2H), 1.32~1.18 (m, 4H), 1.14~1.07 (m, 2H), 0.84 (t, J=7.0 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 170.17, 169.91, 136.81, 135.29, 135.25, 132.91, 128.28, 128.19, 128.05, 118.40, 118.33, 66.67, 61.36, 48.56, 38.70, 31.34, 30.28, 27.28, 22.35, 13.86. HRMS (ESI-TOF) calcd for C28H33O4 [M－H]＋ 433.2384, found 433.2380. HPLC analysis: chiral IC (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=99∶1, 1.0 mL/min, 25 ℃, 210 nm), tR(minor)=15.28 min, tR(major)=16.07 min.
－24.52 (c 0.3, acetone); 1H NMR (400 MHz, CDCl3) δ: 7.37~7.26 (m, 10H), 5.82~5.68 (m, 1H), 5.51 (dt, J=17.0, 10.1 Hz, 1H), 5.20~5.10 (m, 4H), 5.10~5.06 (m, 1H), 5.06~4.94 (m, 3H), 2.66 (d, J=7.3 Hz, 2H), 2.59 (td, J=10.2, 2.3 Hz, 1H), 1.60 (dt, J=10.4, 3.9 Hz, 2H), 1.32~1.18 (m, 4H), 1.14~1.07 (m, 2H), 0.84 (t, J=7.0 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ: 170.17, 169.91, 136.81, 135.29, 135.25, 132.91, 128.28, 128.19, 128.05, 118.40, 118.33, 66.67, 61.36, 48.56, 38.70, 31.34, 30.28, 27.28, 22.35, 13.86. HRMS (ESI-TOF) calcd for C28H33O4 [M－H]＋ 433.2384, found 433.2380. HPLC analysis: chiral IC (250 mm×4.6 mm, 5 µm, V(hexane)∶V(i-PrOH)=99∶1, 1.0 mL/min, 25 ℃, 210 nm), tR(minor)=15.28 min, tR(major)=16.07 min.4.4 Synthesis of 5
To a flame-dried RB charged with a stir bar were added 3a (1.0 equiv.) and 0.5 mL of ethanol. To the vial was added 0.5 mL of an ethanolic solution of KOH (14 mg, 2.5 equiv.). The reaction mixture was stirred for 18 h at room temperature under nitrogen. The reaction mixture was then concentrated to dryness and acidified with 1 mol/L HCl until precipitate stopped appearing. The resulting mixture was diluted with water and then extracted with EtOAc (10 mL×3). The combined organic layers were dried over Na2SO4 and concentrated under reduced pressure to afford 5 as a yellow oil (14.2 mg, 85% yield, B∶L=3.3∶1, 87% ee). Eluent: DCM/MeOH=80∶20. 
＋4.32 (c 0.3, acetone; 1H NMR (400 MHz, CDCl3) δ: 7.90 (s, 3H), 5.64 (dt, J=17.1, 8.4 Hz, 1H), 5.59~5.50 (m, 0.21H), 5.36 (dt, J=9.2, 5.8 Hz, 0.28H), 5.18~5.06 (m, 2H), 3.43 (d, J=8.0 Hz, 1H), 2.80~2.68 (m, 1H), 2.60 (s, 0.34H), 1.98 (p, J=7.0 Hz, 0.60H), 1.43~1.18 (m, 10H), 0.87 (t, J=6.6 Hz, 4H); 13C NMR (101 MHz, CDCl3) 13C NMR (101 MHz, CDCl3) δ: 173.84, 137.49, 118.23, 56.89, 44.58, 32.28, 31.61, 26.82, 22.65, 14.16, 14.14. HRMS (ESI-TOF) calcd for C11H17O4 [M－H]＋ 213.1132, found 213.1128. HPLC analysis: chiral IB N-5 (250 mm×4.6 mm, 5 µm, V(he-xane)∶V(i-PrOH)=80∶20, 1.0 mL/min, 25 ℃, 210 nm), tR(minor)=65.97 min, tR(major)=72.67 min).
＋4.32 (c 0.3, acetone; 1H NMR (400 MHz, CDCl3) δ: 7.90 (s, 3H), 5.64 (dt, J=17.1, 8.4 Hz, 1H), 5.59~5.50 (m, 0.21H), 5.36 (dt, J=9.2, 5.8 Hz, 0.28H), 5.18~5.06 (m, 2H), 3.43 (d, J=8.0 Hz, 1H), 2.80~2.68 (m, 1H), 2.60 (s, 0.34H), 1.98 (p, J=7.0 Hz, 0.60H), 1.43~1.18 (m, 10H), 0.87 (t, J=6.6 Hz, 4H); 13C NMR (101 MHz, CDCl3) 13C NMR (101 MHz, CDCl3) δ: 173.84, 137.49, 118.23, 56.89, 44.58, 32.28, 31.61, 26.82, 22.65, 14.16, 14.14. HRMS (ESI-TOF) calcd for C11H17O4 [M－H]＋ 213.1132, found 213.1128. HPLC analysis: chiral IB N-5 (250 mm×4.6 mm, 5 µm, V(he-xane)∶V(i-PrOH)=80∶20, 1.0 mL/min, 25 ℃, 210 nm), tR(minor)=65.97 min, tR(major)=72.67 min).Supporting Information Experimental procedures, characterization data and NMR spectra. The Supporting Information is available free of charge via the Internet at http://sioc-journal.cn.
(Lu, Y.)