基于去对称化策略合成磷中心手性化合物的研究进展

doi:10.6023/cjoc202406029

摘要/Abstract

有机磷化合物广泛存在于医药、材料、生命、合成等领域, 其中应用最为广泛的是手性磷化合物. 因此, 开展磷中心手性的构建研究一直是有机化学的研究热点和难点. 传统的合成方法主要是通过手性拆分及手性诱导实现. 近年来通过不对称催化实现磷中心的构建得到了迅速的发展. 本综述介绍了近十年来通过去对称化的策略来构建磷中心手性的研究进展, 主要是以官能团如C—H键、羟基、不饱和键的转化及其它一些类型的反应进行分类介绍, 并对该研究领域存在的一些问题和未来发展趋势进行了展望.

关键词: 磷中心手性, 去对称化, C—H键活化

Organophosphorus compounds are extensively utilized in the field of medicine, materials, life sciences, and organic synthesis, among which chiral phosphorus compounds are the most widely used. Therefore, the construction of chiral phosphorus centers has always been the hotspot and challenge in organic synthesis. Traditional synthesis methods are mainly focused on chiral resolution and chiral induction strategies. Recently, the construction of chiral phosphorus centers via asymmetric catalysis has been well developed. The recently development of desymmetrization strategies in the construction of phos- phorus centers is summarized, mainly focused on the transformation of C—H, C=C, C≡C bonds and hydroxyl group. What’s more, the deficiencies of current strategies and the trends of future development have also been discussed.

Key words: P-stereogenic center, desymmetrization, C—H bond activation

引用此文

林国涛, 许健, 宋秋玲. 基于去对称化策略合成磷中心手性化合物的研究进展[J]. 有机化学, 2024, 44(12): 3621-3638.

Guotao Lin, Jian Xu, Qiuling Song. Recent Advances in the Synthesis of P-Stereogenic Compounds via Desymmetrization Strategy[J]. Chinese Journal of Organic Chemistry, 2024, 44(12): 3621-3638.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 38

图1. 含有磷中心手性的活性分子

Figure 1. Biologically molecules containing a P-stereogenic center

图式1. 二甲基膦的不对称去质子化

Scheme 1. Asymmetric deprotonation of dimethylphosphine

图式2. 钯催化C—H键去对称化合成手性磷酰胺

Scheme 2. Pd(II)-catalyzed synthesis of P?stereogenic phosphinamides via desymmetric C—H arylation

图式3. 钯催化分子内芳基邻位C—H键活化去对称化反应

Scheme 3. Pd-catalyzed desymmetrization of intramolecular C—H bond activation in ortho-position of aryl

图式4. 分子内钯催化C—H键芳基化反应机理

Scheme 4. Mechanism of Pd-catalyzed intramolecular C—H arylation

图式5. 钯催化分子内不对称C—H键活化合成手性二苯并膦

Scheme 5. Pd-catalyzed asymmetric C—H bond activation for the synthesis of P-stereogenic dibenzophospholes

图式6. 钯催化C—H键炔基化反应合成手性磷酰胺

Scheme 6. Synthesis of P-stereogenic phosphinamides via Pd(II)-catalyzed C—H alkynylation

图式7. 钯催化C(sp3)—H芳基化反应合成磷手性二烷基磷酰胺

Scheme 7. Pd(II)-catalyzed C(sp3)—H arylation toward P-ste- reogenic dialkylphosphinamides

图式8. Rh催化不对称C—H键活化合成磷手性环磷酰胺

Scheme 8. Rhodium(III)-catalyzed enantiotopic C—H activation enables access to P-chiral cyclic phosphinamides

图式9. 铱催化芳基膦C—H键胺化构建磷手性中心

Scheme 9. Iridium(III)-catalyzed C—H amidation of aryl- phosphoryls leading to a P-stereogenic center

图式10. 铱催化芳基膦氧不对称C—H键胺化反应

Scheme 10. Ir-catalyzed enantioselective C—H amidations of phosphine oxides

图式11. 铱催化C—H键芳基化合成联苯型手性磷化合物

Scheme 11. Ir-catalyzed C—H arylations enables access to P-chiral biaryl phosphine oxides

图式12. 铱催化三级氧化膦C—H键与二芳基炔的偶联反应

Scheme 12. Ir-catalyzed C—H coupling of tertiary substituted phosphine oxides with diarylacetylenes

图式13. 铱催化磷酰胺的间位不对称C—H键硼化反应

Scheme 13. Iridium-catalyzed enantioselective C—H borylation of phosphinamides at m-position

图式14. 铱催化二芳基磷酸酯的不对称C—H键硼化反应

Scheme 14. Iridium-catalyzed enantioselective C—H borylation of diarylphosphinates

图式15. 钴催化芳基磷酰胺C—H键不对称官能团化反应

Scheme 15. Cobalt-catalyzed enantioselective C—H functionalization of arylphosphinamides

图式16. 钴催化不对称C—H键醚化及胺化反应

Scheme 16. Cobalt-catalyzed enantioselective C—H alkoxylation and amination

图式17. 钴/电共催化C—H键不对称醚化反应

Scheme 17. Electrochemical cobalt-catalyzed enantioselective C—H alkoxylation

图式18. 钴/电共催化芳基磷酰胺C—H键不对称官能团化反应

Scheme 18. Electrochemical cobalt-catalyzed enantioselective C—H functionalization of arylphosphinamides

图式19. 钴/电共催化C—H键不对称酯化反应

Scheme 19. Electrochemical cobalt-catalyzed enantioselective C—H esterification

图式20. 脂肪酶催化前手性磷硼烷的去对称化反应

Scheme 20. Lipase-catalyzed desymmetrization of a prochiral phosphine-borane

图式21. 卡宾催化含磷中心手性的双苯酚的去对称化反应

Scheme 21. Carbene-catalyzed desymmetrization of bisphenols bearing a P-stereogenic center

图式22. 双金鸡纳碱催化含磷中心手性的双苯酚的去对称化反应

Scheme 22. Biscinchona alkaloid catalyzd desymmetrization of bisphenols bearing a P-stereogenic center

图式23. 吡啶氧化物催化含磷中心手性的双苯酚的去对称化反应

Scheme 23. Pyridine-N-oxide catalyzed desymmetrization of bisphenols bearing a P-stereogenic center

图式24. 亲电硒试剂催化的去对称环化反应

Scheme 24. Electrophilic selenium-catalyzed desymmetrizing cyclization reaction

图式25. 铑催化二炔基氧化膦的去对称化反应

Scheme 25. Rh-catalyzed desymmetrization of dialkynylphos- phine oxides

图式26. 铜催化含磷手性中心的二炔的去对称化反应

Scheme 26. Copper-catalyzed desymmetrization of diynes bear- ing a P-stereogenic center

图式27. 铥催化二炔基氧化膦的去对称化反应

Scheme 27. Thulium(III)-catalyzed desymmetrization of dialkynylphosphine oxides

图式28. 金催化含磷中心手性的二酚去对称化反应

Scheme 28. Gold-catalyzed desymmetrization of bisphenols bearing a P-stereogenic center

图式29. 钼催化不对称复分解成环反应

Scheme 29. Molybdenum-catalyzed asymmetric ring-closing metathesis

图式30. 铑催化芳基氧化膦的不对称芳基化反应

Scheme 30. Rhodium-catalyzed asymmetric arylation of phospholene oxides

图式31. 铑催化二烯基氧化膦的去对称化反应

Scheme 31. Rhodium-catalyzed desymmetrization of divinyl- phosphine oxides

图式32. 氢键催化磷酰二氯的去对称化反应

Scheme 32. Hydrogen-bond-donor catalysis desymmetrization of phosphonic dichlorides

图式33. 磷酸酯的催化去对称化反应

Scheme 33. Catalytic desymmetrization of phosphonate esters

图式34. 五价磷中心的亲核取代型去对称化反应

Scheme 34. Nucleophilic desymmetrization at phosphorus (V)

图式35. 镍催化手性膦硼烷的合成

Scheme 35. Ni-catalyzed synthesis of P-stereogenic phosphine-boranes

图式36. 镍催化合成手性磷酰肼

Scheme 36. Nickel-catalyzed synthesis of P-stereogenic phosphanyl hydrazine

图式37. 铱催化磷酰胺中氮原子的去对称化反应

Scheme 37. Iridium-catalyzed desymmetrization of phosphonamides at the N atom

参考文献 45

[1]	(a) Rodriguez J. B.; Gallo-Rodriguez C. ChemMedChem 2018, 14, 190. pmid: 28792763
	(b) Dutartre M.; Bayardon J.; Jugé S. Chem. Soc. Rev. 2016, 45, 5771. pmid: 28792763
	(c) Mehellou Y.; Rattan H. S.; Balzarini J. J. Med. Chem. 2018, 61, 2211 doi: 10.1021/acs.jmedchem.7b00734 pmid: 28792763
[2]	(a) Tang W.; Zhang X. Chem. Rev. 2003, 103, 3029. pmid: 21087011
	(b) Fernández-Pérez H.; Etayo P.; Panossian A.; Vidal-Ferran A. Chem. Rev. 2011, 111, 2119. doi: 10.1021/cr100244e pmid: 21087011
	(c) van Leeuwen P. W. N.; Kamer M. P. C. J.; Claver C.; Pàmies O.; Diéguez M. Chem. Rev. 2011, 111, 2077. doi: 10.1021/cr1002497 pmid: 21087011
	((d) Zhang Y.; Zhu S. Acta Chim. Sinica 2023, 81, 777 (in Chinese). pmid: 21087011
	(张艳东, 朱守非, 化学学报, 2023, 81, 777.) doi: 10.6023/A23040125 pmid: 21087011
[3]	(a) Ray A. S.; Fordyce M. W.; Hitchcock M. J. M. Antiviral Res. 2016, 125, 63.
	(b) Wang Y.; Zhang D.; Du G.; Du R.; Zhao J.; Jin Y.; Fu S.; Gao L.; Cheng Z.; Lu Q.; Hu Y.; Luo G.; Wang K.; Lu Y.; Li H.; Wang S.; Ruan S.; Yang C.; Mei C.; Wang Y.; Ding D.; Wu F.; Tang X.; Ye X.; Ye Y.; Liu B.; Yang J.; Yin W.; Wang A.; Fan G.; Zhou F.; Liu Z.; Gu X.; Xu J.; Shang L.; Zhang Y.; Cao L.; Guo T.; Wan Y.; Qin H.; Jiang Y.; Jaki T.; Hayden F. G.; Horby P. W.; Cao B.; Wang C. Lancet 2020, 395, 1569.
	(c) Pilote L.; Abrahamowicz M.; Eisenberg M.; Humphries K.; Behlouli K. H.; Tu J. V. Can. Med. Assoc. J. 2008, 178, 1303.
[4]	(a) Dutartre M.; Bayardon J.; Jugé S. Chem. Soc. Rev. 2016, 45, 5771. pmid: 27479243
	(b) Lemouzy S.; Giordano L.; Hérault D.; Buono G. Eur. J. Org. Chem. 2020, 2020, 3351. pmid: 27479243
	(c) Liu J.; Chen H.; Wang M.; He W.; Yan J. Front. Chem. 2023, 11, 1. pmid: 27479243
[5]	(a) Li H.; Yin L. Chin. J. Org. Chem. 2022, 42, 3183 (in Chinese).
	(李晖, 殷亮, 有机化学, 2022, 42, 3183.) doi: 10.6023/cjoc202208002
	(b) Ye X.; Peng L.; Bao X.; Tan C.-H.; Wang H. Green Synth. Catal. 2021, 2, 6.
[6]	(a) Muci A. R.; Campos K. R.; Evans D. A. J. Am. Chem. Soc. 1995, 117, 9075. pmid: 21510703
	(b) Genet C.; Canipa S. J.; O’Brien P.; Taylor S. J. Am. Chem. Soc. 2006, 128, 9336. pmid: 21510703
	(c) Granander J.; Secci F.; Canipa S. J.; O’Brien P.; Kelly B. J. Org. Chem. 2011, 76, 4794. doi: 10.1021/jo200708e pmid: 21510703
[7]	Qian P.-F.; Li J.-Y.; Zhou Y.-B.; Zhou T.; Shi B.-F. SynOpen 2023, 7, 466.
[8]	Du Z.; Guan J.; Wu G.; Xu P.; Gao L.; Han F. J. Am. Chem. Soc. 2015, 137, 632.
[9]	Qin X.-L.; Li A.; Han F.-S. J. Am. Chem. Soc. 2021, 143, 2994.
[10]	Lin Z.; Wang W.; Yan S.; Duan W. Angew. Chem., Int. Ed. 2015, 54, 6265.
[11]	Liu L.; Zhang A.; Wang Y.; Zhang F.; Zuo Z.; Zhao W.-X.; Feng C.-L.; Ma W. Org. Lett. 2015, 17, 2046.
[12]	Xu G.; Li M.; Wang S.; Tang W. Org. Chem. Front. 2015, 2, 1342.
[13]	Li Z.; Lin Z.; Yan C.; Duan W. Organometallics 2019, 38, 3916.
[14]	Zhou T.; Fan L.; Chen Z.; Jiang M.; Qian P.; Hu X.; Zhang K.; Shi B. Org. Lett. 2023, 25, 5724.
[15]	Wang C.; Zhou T.; Shi B. ACS Catal. 2024, 14, 7213.
[16]	Sun Y.; Cramer N. Angew. Chem., Int. Ed. 2016, 56, 364.
[17]	Gwon D.; Lee D.; Kim J.; Park S.; Chang S. Chem.-Eur J. 2014, 20, 12421.
[18]	Jang Y.; Dieckmann M.; Cramer N. Angew. Chem., Int. Ed. 2017, 56, 15088.
[19]	Jang Y.; Woźniak Ł.; Pedroni J.; Cramer N. Angew. Chem., Int. Ed. 2018, 57, 12901.
[20]	Zhang C.-W.; Hu X.-Q.; Dai Y.-H.; Yin P.; Wang C.; Duan W.-L. ACS Catal. 2022, 12, 193.
[21]	Genov G.; Douthwaite J.; Lahdenper€a A.; Gibson D.; Phipps R. Science 2020, 367, 1246
[22]	Song S.-Y.; Li Y.; Ke Z.; Xu S. ACS Catal. 2021, 11, 13445.
[23]	Yao Q.-J.; Chen J.-H.; Song H.; Huang F.-R.; Shi B-F. Angew. Chem., Int. Ed. 2022, 61, e202202892.
[24]	Chen J.-H.; Teng M.-Y.; Huang F.-R.; Song H.; Wang Z.-K.; Zhuang H.-L.; Wu Y.-J.; Wu X.; Yao Q.-J.; Shi B.-F. Angew. Chem., Int. Ed. 2022, 61, e202210106.
[25]	Zhou G.; Chen J.-H.; Yao Q.-J.; Huang F.-R.; Wang Z.-K.; Shi B.-F. Angew. Chem., Int. Ed. 2023, 62, e202302964.
[26]	Münchow T.; Dana S.; Xu Y.; Yuan B.; Ackermann K. Science 2023, 379, 1036.
[27]	Xia X.-Y.; Zheng C.-D.; Hang Y.-F.; Guo J.-Y.; Liu T.; Song D.-G.; Chen Z.-W.; Zhong W.-F.; Ling F. Green Chem. 2024, 26, 8323.
[28]	Wiktelius D.; Johansson M.; Luthman K.; Kann N. Org. Lett. 2005, 7, 4991. pmid: 16235940
[29]	Huang Z.; Huang X.; Li B.; Mou C.; Yang S.; Song B.; Chi Y. R. J. Am. Chem. Soc. 2016, 138, 7524.
[30]	Yang G.; Li Y.; Li X.; Cheng J. Chem. Sci. 2019, 10, 4322.
[31]	Chen Y.-G.; Hu Y.; Liu J.-Y.; Xie M.-S.; Guo H.-M. Org. Chem. Front. 2023, 20, 6140.
[32]	Qi Z.-C.; Li Y.; Wang J.; Ma L.; Wang G.-W.; Yang S.-D. ACS Catal. 2023, 13, 13301.
[33]	Nishida G.; Noguchi K.; Hirano M.; Tanaka K. Angew. Chem., Int. Ed. 2008, 47, 3410.
[34]	Zhu R.-Y.; Chen L.; Hu X.-S.; Zhou F.; Zhou J. Chem. Sci. 2020, 11, 97.
[35]	Zhang Y.; Zhang F.; Chen L.; Xu J.; Liu X.; Feng X. ACS Catal. 2019, 9, 4834. doi: 10.1021/acscatal.9b00860
[36]	Zheng Y.; Guo L.; Zi W. Org. Lett. 2018, 20, 7039. doi: 10.1021/acs.orglett.8b02982 pmid: 30371092
[37]	Harvey J. S.; Malcolmson S. J.; Dunne K. S.; Meek S. J.; Thompson A. L.; Schrock R. R.; Hoveyda A. H.; Gouverneur V. Angew. Chem., Int. Ed. 2009, 48, 762.
[38]	Lim K.; Hayashi T. J. Am. Chem. Soc. 2017, 139, 8122.
[39]	Wang Z.; Hayashi T. Angew. Chem., Int. Ed. 2018, 57, 1702.
[40]	Forbes C.; Jacobsen E. Science 2022, 376, 1230.
[41]	Formica M.; Rogova T.; Shi H.; Sahara N.; Ferko B.; Farley A.; Christensen K.; Duarte F.; Yamazaki K.; Dixon D. Nat. Chem. 2023, 15, 714.
[42]	Formica M.; Ferko B.; Marsh T.; Davidson T.; Yamazaki K.; Dixon D. Angew. Chem., Int. Ed. 2024, 63, e202400673.
[43]	Wang C.; Huang K.; Ye J.; Duan W. J. Am. Chem. Soc. 2021, 143, 5685
[44]	Wang C.; Yang Q.; Dai Y.; Xiong J.; Zheng Y.; Duan W. Angew. Chem., Int. Ed. 2023, e202313112.
[45]	Zhang X.-L.; Qi X.; Wu Y.-X.; Liu P.; He Y. Cell Rep. Phys. Sci. 2021, 2, 100594.