Kinetic Resolution of Aldehydes Bearing an All-Carbon Quaternary Stereocenter at the α-Position by the Antilla Allylboration

doi:10.6023/cjoc202304015

Abstract

Acyclic aldehydes containing a chiral all-carbon quaternary center at the α-position are important synthons for pharmaceuticals and natural products. The challenges such as steric congestion and conformational flexibility in acyclic systems must be overcome, which constitutes to be a hot and difficult topic in the field of asymmetric catalysis. Such type of structural motif is mainly accessed from the α-C—H functionalization of tertiary aldehydes via enamine catalysis or based on enolate chemistry. Desymmetric and tandem strategies have also been applied for the synthetic task. The discovery of novel synthetic methods is still highly demanding, especially in an organocatalysis manner. Binaphthol (BINOL)-derived chiral phosphoric acids have been demonstrated as efficient bifunctional catalysts in a wide range of organic reactions including the asymmetric allylboration of aldehydes (Antilla allylboration). We envisaged that if racemic α-all-carbon quaternary aldehydes were applied, kinetic resolution of aldehydes through the Antilla allylboration would provide chiral aldehydes and homoallylic alcohols containing an all-carbon quaternary center. The idea was eventually realized by employing 10 mol% (R)-3,3'-bis- (2,4,6-triisopropylphenyl)-1,1'-binaphthyl-2,2'-diylhydrogenphosphate (TRIP) in toluene at –70 ℃. 15 examples of racemic aldehydes bearing electron-rich, electron-neutral and electron-deficient substituents at the phenyl ring, as well as 2-naphthyl group were screened, affording moderate kinetic resolution performance (with an s-factor up to 37.0). The ee values of chiral aldehydes and homoallylic products reached up to 97% and 81%, respectively. This method provides a new route for the synthesis of chiral molecules bearing an all-carbon quaternary stereocenter.

Key words: chiral aldehyde, allylboration, chiral phosphoric acid, all-carbon quaternary center, kinetic resolution

Cite this article

Yuliang Chen, Fengkai He, Siyun Wang, Dingcheng Jia, Yaqun Liu, Yiyong Huang. Kinetic Resolution of Aldehydes Bearing an All-Carbon Quaternary Stereocenter at the α-Position by the Antilla Allylboration[J]. Chinese Journal of Organic Chemistry, 2023, 43(12): 4294-4302.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 4

References 29

[1]	(a) Long R.; Huang J.; Gong J.; Yang Z. Nat. Prod. Rep. 2015, 32, 1584. doi: 10.1039/C5NP00046G
	(b) Zeng X.-P.; Cao Z.-Y.; Wang Y.-H.; Zhou F.; Zhou J. Chem. Rev. 2016, 116, 7330. doi: 10.1021/acs.chemrev.6b00094
	(c) Das J. P.; Marek I. Chem. Commun. 2011, 47, 4593. doi: 10.1039/c0cc05222a
	(c) Qi H.-B.; Han K.-M.; Chen S.-F. Chin. J. Chem. 2021, 39, 2699. doi: 10.1002/cjoc.v39.10
	(d) He X.-L.; Ye K.-Y.; Chin. J. Org. Chem. 2022, 42, 3434. (in Chinese) doi: 10.6023/cjoc202200060
	(何星磊, 叶克印, 有机化学, 2022, 42, 3434.) doi: 10.6023/cjoc202200060
[2]	(a) Jung M. E.; D'Amico D. C. J. Am. Chem. Soc. 1995, 117, 7379. doi: 10.1021/ja00133a011
	(b) Bando T.; Shishido K. Chem. Commun. 1996, 1357.
	(c) Corey E. J.; Guzman-Perez A. Angew. Chem., Int. Ed. 1998, 37, 388. doi: 10.1002/(ISSN)1521-3773
[3]	Trost B. M.; Hung C.-I. J.; Jiao Z.-W. J. Am. Chem. Soc. 2019, 141, 16085. doi: 10.1021/jacs.9b08441
[4]	Vital P.; Tanner D. Org. Biomol. Chem. 2006, 4, 4292. doi: 10.1039/b612578f
[5]	Kita Y.; Furukawa A.; Futamura J.; Ueda K.; Sawama Y.; Hamamoto H.; Fujioka H. J. Org. Chem. 2001, 66, 8779. pmid: 11749606
[6]	Wilson M. S.; Woo J. C. S.; Dake G. R. J. Org. Chem. 2006, 71, 4237. doi: 10.1021/jo0604585
[7]	Sonawane R. P.; Jheengut V.; Rabalakos C.; Larouche-Gauthier R.; Scott H. K.; Aggarwal V. K. Angew. Chem., Int. Ed. 2011, 50, 3760. doi: 10.1002/anie.v50.16
[8]	Lee M.; Kim D. H. Bioorg. Med. Chem. 2002, 10, 913. doi: 10.1016/S0968-0896(01)00340-6
[9]	(a) Mase N.; Tanaka F.; Barbas III C. F. Angew. Chem., Int. Ed. 2004, 43, 2420. doi: 10.1002/anie.v43:18 pmid: 28238267
	(b) Mukherjee S.; List B. J. Am. Chem. Soc. 2007, 129, 11336. pmid: 28238267
	(c) Brown A. R.; Kuo W.-H.; Jacobsen E. N. J. Am. Chem. Soc. 2010, 132, 9286. doi: 10.1021/ja103618r pmid: 28238267
	(d) Krautwald S.; Sarlah D.; Schafroth M. A.; Carreira E. M. Science 2013, 340, 1065. doi: 10.1126/science.1237068 pmid: 28238267
	(e) List B.; Čorić I.; Grygorenko O. O.; Kaib P. S. J.; Komarov I.; Lee A.; Leutzsch M.; Pan S. C.; Tymtsunik A. V.; van Gemmeren M. Angew. Chem., Int. Ed. 2014, 53, 282. doi: 10.1002/anie.v53.1 pmid: 28238267
	(f) Zhou H.; Wang Y.-N.; Zhang L.; Cai M.; Luo S.-Z. J. Am. Chem. Soc. 2017, 139, 3631. doi: 10.1021/jacs.7b00437 pmid: 28238267
	(g) Cruz F. A.; Dong V. M. J. Am. Chem. Soc. 2017, 139, 1029. doi: 10.1021/jacs.6b10680 pmid: 28238267
[10]	(a) Mo X.-B.; Hall D. G. J. Am. Chem. Soc. 2016, 138, 10762. doi: 10.1021/jacs.6b06101
	(b) Wright T. B.; Evans P. A. J. Am. Chem. Soc. 2016, 138, 15303. doi: 10.1021/jacs.6b10099
	(c) Trost B. M.; Hung C.-I.; Saget T.; Gnanamani E. Nat. Catal. 2018, 1, 523. doi: 10.1038/s41929-018-0093-6
	(d) Trost B. M.; Zuo Z.-J.; Wang Y.-L.; Schultz J. E. ACS Catal. 2020, 10, 9496. doi: 10.1021/acscatal.0c02861
	(e) Zhang W.-Q.; Shen H.-C. ACS Catal. 2021, 11, 11849. doi: 10.1021/acscatal.1c03449
	(f) Pan Z.-J.; Li W.-B.; Zhu S.; Liu F.; Wu H.-H.; Zhang J.-L. Angew. Chem., Int. Ed. 2021, 60, 18542. doi: 10.1002/anie.v60.34
[11]	Meng J.; Fan L.-F.; Han Z.-Y.; Gong L.-Z. Chem 2018, 4, 1047. doi: 10.1016/j.chempr.2018.03.010
[12]	Xu P.-W.; Liu S.-H.; Huang Z.-X. J. Am. Chem. Soc. 2022, 144, 6918. doi: 10.1021/jacs.2c01380
[13]	Gao L.; Kang B. C.; Ryu D. H. J. Am. Chem. Soc. 2013, 135, 14556. doi: 10.1021/ja408196g
[14]	Xu J.; Song Y.; Yang J.; Yang B.; Su Z.; Lin L.; Feng X. Angew. Chem., Int. Ed. 2023, 62, e202217887. doi: 10.1002/anie.v62.13
[15]	Qiu Z.-W.; Long L.; Zhu Z.-Q.; Liu H.-F.; Pan H.-P.; Ma A.-J.; Peng J.-B.; Wang Y.-H.; Gao H.; Zhang X.-Z. ACS. Catal. 2022, 12, 13282. doi: 10.1021/acscatal.2c03879
[16]	Uraguchi D.; Terada M. J. Am. Chem. Soc. 2004, 126, 5356. pmid: 15113196
[17]	Akiyama T.; Itoh J.; Yokota K.; Fuchibe K. Angew. Chem., Int. Ed. 2004, 43, 1566. doi: 10.1002/anie.v43:12
[18]	(a) Xia Z.-L.; Xu-Xu Q.-F.; Zheng C.; You S.-L. Chem. Soc. Rev. 2020, 49, 286. doi: 10.1039/C8CS00436F pmid: 34876929
	(b) Maji R.; Mallojjala S. C.; Wheeler S. E. Chem. Soc. Rev. 2018, 47, 1142. doi: 10.1039/C6CS00475J pmid: 34876929
	(c) Parmar D.; Sugiono E.; Raja S.; Rueping M. Chem. Rev. 2014, 114, 9047. doi: 10.1021/cr5001496 pmid: 34876929
	(d) Woldegiorgis A. G.; Lin X.-F. Beilstein J. Org. Chem. 2021, 17, 2729. doi: 10.3762/bjoc.17.185 pmid: 34876929
	(e) Corte X. D.; Marigorta E. M. D.; Palacios F.; Vicario J.; Maestro A. Org. Chem. Front. 2022, 9, 6331. doi: 10.1039/D2QO01209J pmid: 34876929
	(f) Da B.-C.; Xiang S.-H.; Li S.-Y.; Tan B. Chin. J. Chem. 2021, 39, 1787. doi: 10.1002/cjoc.v39.7 pmid: 34876929
	(g) Shao Y.-D.; Cheng D.-J. ChemCatChem 2021, 13, 1271. doi: 10.1002/cctc.v13.5 pmid: 34876929
	(h) Woldegiorgis A. G.; Suleman M.; Lin X.-F. Eur. J. Org. Chem. 2022, 2022, e202200624. doi: 10.1002/ejoc.v2022.34 pmid: 34876929
[19]	(a) Liu W.; Yang X. Asian J. Org. Chem. 2021, 10, 692. doi: 10.1002/ajoc.v10.4
	(b) Petersen K. S. Asian J. Org. Chem. 2016, 5, 308. doi: 10.1002/ajoc.v5.3
[20]	(a) Zhu G.; Li Y.; Bao G.; Sun W.; Huang L.; Hong L.; Wang R. ACS Catal. 2018, 8, 1810. doi: 10.1021/acscatal.7b03268
	(b) Yamanaka M.; Hoshino M.; Katoh T.; Mori K.; Akiyama T. Eur. J. Org. Chem. 2012, 4508.
[21]	Zhu G.-M.; Bao G.-J.; Li Y.-P.; Sun W.-S.; Li J.; Hong L.; Wang R. Angew. Chem., Int. Ed. 2017, 56, 5332. doi: 10.1002/anie.v56.19
[22]	Shimoda Y.; Yamamoto H. J. Am. Chem. Soc. 2017, 139, 6855. doi: 10.1021/jacs.7b03592
[23]	(a) James B. R.; Young C. G. J. Organomet. Chem. 1985, 285, 321. doi: 10.1016/0022-328X(85)87377-0 pmid: 12197729
	(b) Tanaka K.; Fu G. C. J. Am. Chem. Soc. 2002, 124, 10296. pmid: 12197729
[24]	Jain P.; Antilla J. C. J. Am. Chem. Soc. 2010, 132, 11884. doi: 10.1021/ja104956s
[25]	For reviews, see: (a) Barrio, P.; Rodríguez, E.; Fustero, S. Chem. Rec. 2016, 16, 2046. doi: 10.1002/tcr.v16.4
	(b) Sedgwick D. M.; Grayson M. N.; Fustero S.; Barrio P. Synthesis 2018, 50, 1935. doi: 10.1055/s-0036-1589532
	For selected examples see:
	(c) Gao S.; Duan M.; Andreola L. R.; Yu P.; Wheeler S. E.; Houk K. N.; Chen M. Angew. Chem., Int. Ed. 2022, 61, e202208908. doi: 10.1002/anie.v61.41
	(d) Gao S.; Duan M.; Liu J.; Yu P.; Houk K. N.; Chen M. Angew. Chem., Int. Ed. 2021, 60, 24096. doi: 10.1002/anie.v60.45
	(e) Gao S.; Duan M.; Houk K. N.; Chen M. Angew. Chem., Int. Ed. 2020, 59, 10540. doi: 10.1002/anie.v59.26
	(f) Gao S.; Duan M.; Shao Q.; Houk K. N.; Chen M. J. Am. Chem. Soc. 2020, 142, 18355. doi: 10.1021/jacs.0c04107
[26]	(a) Huang Y.-Y.; Yang X.; Lv Z.-C.; Cai C.; Kai C.; Pei Y.; Feng Y. Angew. Chem., Int. Ed. 2015, 54, 7299. doi: 10.1002/anie.v54.25
	(b) Yang X.; Pang S.; Cheng F.; Zhang Y.; Lin Y.-W.; Yuan Q.; Zhang F.-L.; Huang Y.-Y. J. Org. Chem. 2017, 82, 10388. doi: 10.1021/acs.joc.7b01856
	(c) Zhang Y.-L.; He B.-J.; Xie Y.-W.; Wang Y.-H.; Wang Y.-L.; Shen Y.-C.; Huang Y.-Y. Adv. Synth. Catal. 2019, 361, 3074. doi: 10.1002/adsc.v361.13
	(d) Zhang Y.-L.; Zhao Z.-N.; Li W.-L.; Li J.-J.; Kalita S. J.; Schneider U.; Huang Y.-Y. Chem. Commun. 2020, 56, 10030. doi: 10.1039/D0CC00367K
[27]	Lu Y.; Kriche M. J. Org. Lett. 2009, 11, 3108. doi: 10.1021/ol901096d
[28]	(a) Sullivan J. M. WO 2000007968, 2000.
	(b) Coxon T. J.; Fernández M.; Barwick-Silk J.; McKay A. I.; Britton L. E.; Weller A. S.; Willis M. C. J. Am. Chem. Soc. 2017, 139, 10142. doi: 10.1021/jacs.7b05713
[29]	(a) Klussmann M.; List B.; Ratjen L.; Hoffmann S.; Wakchaure V.; Goddard R. Synlett 2010, 2189.
	(b) Kobayashi S.; Kusakabe K.; Komiyama S.; Ishitani H. J. Org. Chem. 1999, 64, 4220. doi: 10.1021/jo9902300

Entry	Catalyst (x mol%)	Solvent	Temp./℃	Time/h	Chiral-1a		3a			C/%^f	s^g
Entry	Catalyst (x mol%)	Solvent	Temp./℃	Time/h	Yield^b/%	ee₁^c/%	Yield^b/%	dr^d	ee₂^e/%	C/%^f	s^g
1	(R)-CPA-3 (6)	Toluene	–60	21	45	39	47	>20∶1	50	0.44	4.3
2	(R)-CPA-3 (6)	CH₂Cl₂	–60	29	55	9	41	19.6∶1	18	0.33	1.6
3	(S)-CPA-3 (6)	Toluene	–60	21	44	–37	26	11∶1	–13	0.74	1.8
4	(S)-CPA-3 (6)	CH₂Cl₂	–60	45	41	–9	49	>20∶1	–44	0.17	2.8
5	(R)-CPA-3 (10)	Toluene	–70	16	44	43	34	>20∶1	63	0.41	6.7
6	(R)-CPA-3 (10)	CH₂Cl₂,	–70	36	57	7	27	>20∶1	17	0.29	1.5
7	(S)-CPA-3 (10)	Toluene	–70	21	52	–22	36	>20∶1	–29	0.43	2.2
8	(R)-CPA-4 (10)	Toluene	–70	72	29	30	39	15∶1	44	0.41	3.4
9	(R)-CPA-5 (10)	Toluene	–70	4	35	0	37	9∶1	0	0	0

Entry	Catalyst (x mol%)	Solvent	Temp./℃	Time/h	Chiral-1a		3a			C/%^f	s^g
Entry	Catalyst (x mol%)	Solvent	Temp./℃	Time/h	Yield^b/%	ee₁^c/%	Yield^b/%	dr^d	ee₂^e/%	C/%^f	s^g
1	(R)-CPA-3 (6)	Toluene	–60	21	45	39	47	>20∶1	50	0.44	4.3
2	(R)-CPA-3 (6)	CH₂Cl₂	–60	29	55	9	41	19.6∶1	18	0.33	1.6
3	(S)-CPA-3 (6)	Toluene	–60	21	44	–37	26	11∶1	–13	0.74	1.8
4	(S)-CPA-3 (6)	CH₂Cl₂	–60	45	41	–9	49	>20∶1	–44	0.17	2.8
5	(R)-CPA-3 (10)	Toluene	–70	16	44	43	34	>20∶1	63	0.41	6.7
6	(R)-CPA-3 (10)	CH₂Cl₂,	–70	36	57	7	27	>20∶1	17	0.29	1.5
7	(S)-CPA-3 (10)	Toluene	–70	21	52	–22	36	>20∶1	–29	0.43	2.2
8	(R)-CPA-4 (10)	Toluene	–70	72	29	30	39	15∶1	44	0.41	3.4
9	(R)-CPA-5 (10)	Toluene	–70	4	35	0	37	9∶1	0	0	0

手性磷酸催化α-全碳季碳醛的不对称烯丙基化动力学拆分