手性螺环缩酮化合物的不对称催化合成研究进展

doi:10.6023/cjoc202205001

摘要/Abstract

螺环缩酮是一类结构独特的螺环骨架, 其作为核心结构单元广泛存在于天然产物、生物活性分子和优势手性配体中, 发展其高效的合成方法一直以来都是有机化学领域的研究热点. 尤其是近10年来, 手性螺环缩酮化合物的催化不对称合成取得了重要突破. 根据反应类型划分, 总结了手性螺环缩酮化合物的催化不对称合成研究进展, 并对该领域的研究前景进行了展望.

关键词: 不对称催化, 对映选择性, 螺环缩酮

As an unique spiro skeleton, spiroketals are ubiquitous motifs in many natural products, biologically active molecules, and privileged chiral ligands. The development of efficient synthetic methods for the preparation of spiroketals has long been a hot research topic in organic synthesis. In particular, the remarkable advances regarding the catalytic asymmetric synthesis of chiral spiroketals have been achieved over the past decade. The progress in the field of catalytic asymmetric synthesis of chiral spiroketals is summarized according to the reaction types. The future development direction of this field is also prospected.

Key words: asymmetric catalysis, enantioselectivity, spiroketals

引用此文

闫辉, 张曼, 李琳, 胡腾, 杨武林. 手性螺环缩酮化合物的不对称催化合成研究进展[J]. 有机化学, 2022, 42(11): 3640-3657.

Hui Yan, Man Zhang, Lin Li, Teng Hu, Wulin Yang. Advances in the Catalytic Asymmetric Synthesis of Chiral Spiroketals[J]. Chinese Journal of Organic Chemistry, 2022, 42(11): 3640-3657.

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图/表 31

图式1. 含有手性螺环缩酮骨架的天然产物和生物活性分子

Scheme 1. Representative natural products and biologically active molecules containing chiral spiroketal skeletons

图式2. 含有手性螺环缩酮骨架的手性配体

Scheme 2. Selected examples of chiral ligands containing chiral spiroketal skeletons

图式3. [6,6]-螺环缩酮四种不同的空间构象

Scheme 3. Four different spatial conformations of [6,6]- spiroketal

图式4. 新型磷酰胺催化不对称分子内螺环缩酮化反应和反应机理

Scheme 4. Asymmetric intramolecular spiroketalization catalyzed by novel phosphoramide and reaction mechanism

图式5. 手性磷酸催化不对称分子内螺环缩酮化反应

Scheme 5. Chiral phosphoric acid-catalyzed asymmetric intramolecular spiroketalization

图式6. 手性铱络合物催化不对称氢化/螺环缩酮化合成手性螺环缩酮化合物

Scheme 6. Synthesis of chiral spiroketals via chiral iridium complex catalyzed asymmetric hydrogenation/spiroketalization

图式7. 苄基保护的苯酚衍生物经过不对称氢化/脱保护/螺环缩酮反应合成手性螺环缩酮

Scheme 7. Synthesis of spiroketals via asymmetric hydrogenation of Bn-protected bis(2-hydroxyarylidenes) followed by deprotection-spiroketalization process

图式8. 以二芳基亚烷基丙酮为原料不对称构建[6,6]-二苯并螺环缩酮骨架

Scheme 8. Asymmetric construction of bisbenzannulated [6,6]-spiroketal skeletons from diarylideneacetones

图式9. 一锅法对映选择性合成螺环缩酮化合物

Scheme 9. One-pot enantioselective synthesis of spiroketals

图式10. Bistramide A的全合成

Scheme 10. Total synthesis of Bistramide A

图式11. 金/手性磷酸催化分子内反应合成手性螺环缩酮化合物

Scheme 11. Gold/CPA catalyzed intramolecular reaction to synthesize chiral spiroketals

图式12. 有机催化不对称分子内半缩醛化/Michael加成串联反应合成手性螺环缩酮

Scheme 12. Organocatalytic asymmetric intramolecular hemiacetalization/Michael addition cascade reaction to synthesize chiral spiroketals

图式13. 有机催化不对称分子内亲核取代反应合成二苯并螺环缩酮化合物

Scheme 13. Organocatalytic asymmetric intramolecular nucleophilic substitution reaction to synthesize bisbenzannulated spiroketals

图式14. 铱催化不对称分子内半缩醛化/烯丙基取代串联反应合成手性螺环缩酮

Scheme 14. Ir-catalyzed asymmetric intramolecular hemiacetalization/allylic substitution cascade reaction to synthesize chiral spiroketals

图式 15. (＋)-Broussonetine H的全合成

Scheme 15. Total synthesis of (＋)-Broussonetine H

图式16. 有机催化分子内半缩醛化/氧杂Michael加成串联反应合成手性螺环缩酮

Scheme 16. Organocatalytic intramolecular hemiacetalization/oxa-Michael addition cascade reaction to synthesize chiral spiroketals

图式17. 分子内半缩醛化/氧杂Michael加成串联反应合成手性[5,6]-苯并螺环缩酮

Scheme 17. Intramolecular hemiacetalization/oxa-Michael addition cascade reaction to synthesize chiral [5,6]-aromatic spiroketals

图式18. 苯酚衍生物经氧化/半缩醛化/氧杂Michael加成合成手性螺环缩酮化合物

Scheme 18. Asymmetric synthesis of spiroketals via oxidation/hemiacetalization/oxa-Michael addition of phenol derivatives

图式19. 烯烃酮酸参与的催化不对称卤环化串联反应合成手性螺环缩酮和反应机理

Scheme 19. Catalytic asymmetric halocyclization cascade reaction of olefinic keto-acids to synthesize chiral spiroketals and reaction mechanism

图式20. 有机催化不对称合成同时具有中心手性和轴手性的螺环缩酮内酯化合物

Scheme 20. Organocatalytic enantioselective synthesis of spiroketal lactones bearing axial and central chirality

图式21. 路易斯碱催化不对称分子内环化反应合成手性螺环缩酮

Scheme 21. Lewis base catalyzed asymmetric intramolecular cyclization to synthesize chiral spiroketals

图式22. 通过杂Diels-Alder反应合成手性螺环缩酮

Scheme 22. Catalytic asymmetric synthesis of chiral spiroketals via hetero-Diels-Alder reaction

图式23. 金/手性磷酸催化不对称串联反应合成手性螺环缩酮及反应机理

Scheme 23. Synthesis of chiral spiroketals through gold/CPA-catalyzed asymmetric cascade reaction and the reaction mechanism

图式24. 炔醇、乙醛酸和芳香胺参与的三组分串联反应合成手性螺环缩酮及反应机理

Scheme 24. Asymmetric synthesis of chiral spiroketals through three-component cascade reaction between alkynols, anilines and glyoxylic acid and reaction mechanism

图式25. 金/镍接力催化不对称合成手性螺环缩酮和螺缩醛胺化合物及反应机理

Scheme 25. Au/Ni relay catalysis enables asymmetric synthesis of spiroketals and spiroaminals and reaction mechanism

图式26. 金/铑接力催化不对称合成手性螺环缩酮和螺缩醛胺化合物

Scheme 26. Gold(I)/chiral Rh(III) Lewis acid relay catalysis enables asymmetric synthesis of spiroketals and spiroaminals

图式27. 金/铱催化不对称串联反应合成手性螺环缩酮和螺缩醛胺化合物及其应用

Scheme 27. Au/Ir catalyzed asymmetric cascade reaction to synthesize chiral spiroketals and spiroamines and the application

图式28. 金/铱催化不对称串联反应的反应机理

Scheme 28. Reaction mechanism of Au/Ir catalyzed asymmetric cascade reaction

图式29. 金/镁协同催化不对称串联反应合成手性[6,6]-螺环缩酮及反应机理

Scheme 29. Au/Mg co-catalyzed asymmetric cascade reaction to synthesize chiral [6,6]-spiroketals and reaction mechanism

图式30. 环丙化/重排串联反应合成手性螺环缩酮化合物

Scheme 30. Synthesis of chiral spiroketals through cyclopropionation/rearrangement cascade reaction

图式31. 环丙化/重排串联反应合成手性螺环缩酮化合物的反应机理

Scheme 31. Reaction mechanism of chiral spiro ketal compounds synthesized by cyclopropylation/rearrangement series reaction

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