P-手性膦氧化物的不对称合成研究进展

doi:10.6023/cjoc202212024

摘要/Abstract

手性有机膦化合物在配体、催化剂以及生物活性分子等领域有着广泛的应用. 因此, 通过不对称合成高效构建含P-手性核心骨架化合物吸引了众多化学家的深入研究, 为丰富手性有机膦配体库以及潜在药用活性分子已起到了至关重要的促进作用. 由于五价膦氧化物相对于三价有机膦化合物更稳定且可通过一步还原即可得到三价有机膦化合物, 针对P-手性五价膦氧化合物的不对称合成也因此尤为受到关注, 并快速发展. 基于此, 并针对已报道的相关综述的具体情况, 总结了近三年来不对称合成P-手性膦氧化物的进展, 依据合成策略的不同, 分为手性助剂协助分离、催化去对称化、催化不对称合成、催化动力学拆分或动态动力学不对称转化以及酶催化五个方面进行阐释与讨论.

关键词: P-手性膦氧化物, 有机膦配体, 不对称合成, 不对称催化, 动力学拆分

Enantioenriched organophosphates are ubiquitous in a large array of chiral ligands, chiral catalysts and bioactive molecules. Over the past few decades, synthetic chemists have contributed substantial efforts to develop the efficient methodologies for the construction of P-chiral phosphine derivatives, considerably enriching the arsenal of chiral organophosphine ligands and the promising pharmaceutical molecules. Among them, a number of works are focused on the synthesis of P-chiral phosphine oxides because it is more stability than trivalent phosphines and the convenient reduction. In view of the rapid progress in this area and the currently available reviews, the progress in the last three years is summarized and discussed, namely from 2020 to 2022. The description of the synthetic strategy is divided into five segments, involving asymmetric induction, catalytic desymmetrization, catalytic asymmetric synthesis, catalytic kinetic resolution or dynamic kinetic asymmetric transformation, and enzyme catalysis.

Key words: P-chiral phosphine oxides, organic phosphine ligands, asymmetric synthesis, asymmetric catalysis, kinetic resolution

引用此文

罗诚, 尹艳丽, 江智勇. P-手性膦氧化物的不对称合成研究进展[J]. 有机化学, 2023, 43(6): 1963-1976.

Cheng Luo, Yanli Yin, Zhiyong Jiang. Recent Advances in Asymmetric Synthesis of P-Chiral Phosphine Oxides[J]. Chinese Journal of Organic Chemistry, 2023, 43(6): 1963-1976.

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图/表 23

图式1. 手性膦配体

Scheme 1. Chiral phosphine ligands

图式2. 利用手性助剂合成P-手性双膦配体

Scheme 2. Synthesis of P-chiral diphosphine ligands assisted with chiral auxuliary

图式3. P-手性膦氧化物合成策略

Scheme 3. Synthesis strategy of P-chiral phosphine oxide

图式4. 手性氨基醇协助实现P-手性膦氧化物的合成

Scheme 4. Synthesis of P-chiral phosphine oxide assisted by chiral amino alcohols

图式5. 可见光诱导合成P-手性膦氧化物

Scheme 5. Visible light induced synthesis of P-chiral phosphine oxides

图式6. BINOL为手性助剂构建含轴手性的P-手性膦氧化物

Scheme 6. Construction of P-chiral phosphine oxide containing axial chirality using BINOL as chiral auxiliary

图式7. 不对称卤化构建P-手性膦氧化物

Scheme 7. Construction of P-chiral phosphine oxide by asymmetric halogenation

图式8. 不对称溴化化构建P-手性膦氧化物

Scheme 8. Construction of P-chiral phosphine oxide via asymmetric bromination

图式9. 不对称硼化构建P-手性膦氧化物

Scheme 9. Construction of P-chiral phosphine oxides by asymmetric boration

图式10. 手性酰胺和非手性Cp*Ir催化去对称化构建含轴手性P-手性膦氧化物

Scheme 10. Catalytic desymmetry for synthesis of axially and P-chiral phosphine oxides by a chiral amide and an achiral Cp*Ir

图式11. Co/Salax催化碳氢烷氧基化/氨基化构建P-手性膦氧化物

Scheme 11. Construction of P-chiral phosphine oxides by cobalt/salax-catalyzed alkoxylation/amination

图式12. 膦酸酯和炔烃催化不对称构建P-手性膦氧化物

Scheme 12. Asymmetric construction of P-chiral phosphine oxides of phosphonates and alkynes

图式13. 通过二级膦氧化物高化学、区域和对映选择性构建P-手性烯基TPOs

Scheme 13. Highly chemo-, regio-, and enantio-selective construction of P-chiral alkenylphosphine oxides using secondary phosphine oxides

图式14. 镍催化对映选择性烯丙基烷基化

Scheme 14. Ni-catalyzed enantioselective allyl alkylation

图式15. 镍催化的二级膦氧化物的对映选择性苄基化

Scheme 15. Nickel catalyzed enantioselective benzylation of SPOs

图式16. 钴催化二级膦氧化物的不对称烷基化

Scheme 16. Asymmetric alkylation of secondary phosphine oxides catalyzed by chiral cobalt complex

图式17. 镍催化共轭烯炔的不对称氢膦酰化

Scheme 17. Ni-catalyzed asymmetric hydrophosphinylation of conjugated enynes

图式18. 镍催化炔丙基取代物对映选择性合成P-手性联烯基膦氧化物

Scheme 18. Enantioselective synthesis of P-stereogenic alenylphosphine oxides through Ni-catalysed propargylic substituion

图式19. Le-Phos催化动力学拆分合成P-手性SPOs和TPOs

Scheme 19. Access to P-chiral sec- and tert-phosphine oxides enabled by Le-Phos catalyzed kinetic resolution

图式20. Pd/Xiao-Phos催化SPOs动力学拆分

Scheme 20. Pd/Xiao-Phos-catalyzed kinetic resolution of SPOs

图式21. 铜催化DYKAT构建环状P-手性膦氧化物

Scheme 21. Copper catalyzed DYKAT construction of cyclic P-chiral phosphine oxide

图式22. 酶催化合成瑞德西韦

Scheme 22. Enzymatic catalytic synthesis of remdesivir

图式23. 酶催化去对称化构建膦氧/硫化物

Scheme 23. Enzymatic desymmetry construction of phosphine oxides or sulfides

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