手性螺环双氮配体在过渡金属催化中的应用进展

doi:10.6023/cjoc202210010

摘要/Abstract

手性螺环是配体的优势骨架, 基于螺环结构配体的研究有力地促进了不对称催化领域的发展. 此综述针对基于手性螺环骨架的双氮配体, 按照螺环骨架的类型进行分类, 分别讨论了螺[4.4]壬烷双异噁唑啉(SPRIX)、螺二氢茚双噁唑啉(SpiroBox)、螺二色满双胺(SPANamine)或者双噁唑啉(SPANBox), 以及螺环四氢吡咯-噁唑啉(SPDO)的合成和在过渡金属催化中的应用. 尽管和功能强大、用途广泛的手性螺环膦配体相比, 螺环双氮配体的种类和应用研究还比较有限, 但是这些配体在酸性和(或)氧化反应条件下良好的稳定性以及在催化杂-氢键卡宾插入反应中优异的活性和选择性等特点, 为今后发展新的不对称催化体系提供了重要借鉴.

关键词: 手性螺环配体, 双氮配体, 不对称合成, 过渡金属催化

Chiral spiro skeletons are recognized as a class of “privileged structures” of ligands. Studies toward these spiro ligands have significantly advanced the field of asymmetric catalysis. Bisnitrogen ligands bearing chiral spiro skeletons are reviewed and categorized according to the type of spirocyclic skeletons, including spiro[4.4]nonane-based bis(isoxazoline) ligands (SPRIX), spirobiindane-based bis(oxazoline) ligands (SpiroBox), spirobi(chroman)-based bis(amine) or bis(oxazoline) ligands (SPANamine or SPANBox), and spirocyclic pyrrolidine oxazoline ligands (SPDO). The synthesis and application of these four types of ligands and their applications in transition-metal catalysis are discussed in detail. Compared with the powerful and widely utilized chiral sprio phosphine ligands, the availability and application of spiro bisnitrogen ligands are relatively limited. Nevertheless, their features such as stability under acidic conditions and/or in the presence of an oxidant, superior capability of catalyzing carbene insertion into heteroatom-hydrogen bonds, provide insights and inspirations to the development of novel catalytic systems in asymmetric synthesis.

Key words: chiral spiro ligands, bisnitrogen ligands, asymmetric synthesis, transition-metal catalysis

引用此文

胡旭东, 张鑫亮, 刘文博. 手性螺环双氮配体在过渡金属催化中的应用进展[J]. 有机化学, 2022, 42(10): 3102-3117.

Xudong Hu, Xinliang Zhang, Wenbo Liu. Advances of Chiral Spiro Skeleton-Based Bisnitrogen Ligands in Transition-Metal Catalysis[J]. Chinese Journal of Organic Chemistry, 2022, 42(10): 3102-3117.

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图/表 27

图1. 基于手性螺环骨架双氮配体的代表性结构

Figure 1. Representative structures of chiral spiro skeleton- based bisnitrogen ligands

图式1. 螺环双异噁唑啉配体(SPRIX)的合成以及在钯催化的Wacker类反应中的催化应用

Scheme 1. Synthesis of spiro bis(isoxazoline) ligands (SPRIX) and their applications in Pd-catalyzed Wacker-typed reactions

图式2. 螺环双异噁唑啉配体(SPRIX)在钯催化的串联环化反应中的应用

Scheme 2. Application of spiro bis(isoxazoline) ligands (SPRIX) in Pd-catalyzed tandem cyclization reaction

图式3. Pd/SPRIX催化体系在不对称氨钯化插羰反应和氧钯化反应中的应用

Scheme 3. Applications of Pd/SPRIX catalytic system in asymmetric amino-palladation and oxo-palladation reactions

图式4. Pd/SPRIX催化烯炔不对称氧化环化串联反应

Scheme 4. Pd/SPRIX-catalyzed asymmetric oxidative cyclization of enynes

图式5. Pd/SPRIX催化不对称吲哚碳氢活化/烷基化反应

Scheme 5. Pd/SPRIX-catalyzed asymmetric C—H activation/alkylation of indoles

图式6. 基于螺[4.4]壬烷骨架的双吡唑和双噁唑啉配体

Scheme 6. Spiro[4.4]nonane-based bis(oxazoline) and bis(pyrazole) ligands

图式7. 基于螺二氢茚骨架双噁唑啉的合成及N—H键插入反应应用

Scheme 7. Synthesis of spirobiindane-based bis(oxazoline) ligands and their applications in insertion of carbenoids into N—H bonds

图式8. Cu/SpiroBox催化的卡宾N—H键不对称插入反应

Scheme 8. Cu/SpiroBox-catalyzed enantioselective insertion of carbenoids into N—H bonds

图式9. Cu/SpiroBox催化卡宾对水分子O—H键的不对称插入反应

Scheme 9. Cu/SpiroBox-catalyzed enantioselective insertion of carbenoids into O—H bonds of water

图式10. Cu/SpiroBox催化卡宾对醇O—H键的不对称插入反应

Scheme 10. Cu/SpiroBox-catalyzed enantioselective insertion of carbenoids into O—H bonds of alcohols

图式11. Cu/SpiroBox催化卡宾对S—H键的不对称插入反应

Scheme 11. Cu/SpiroBox-catalyzed enantioselective insertion of carbenoids into S—H bonds

图式12. Fe/SpiroBox催化卡宾对O—H键的不对称插入反应

Scheme 12. Fe/SpiroBox-catalyzed enantioselective insertion of carbenoids into O—H bonds

图式13. Pd/SpiroBox催化卡宾对苯酚O—H键的不对称插入反应

Scheme 13. Fe/SpiroBox-catalyzed enantioselective insertion of carbenoids into O—H bonds of phenols

图式14. Cu/SIDIM催化卡宾对Si—H键的不对称插入反应

Scheme 14. Cu/SIDIM-catalyzed enantioselective insertion of carbenoids into Si—H bonds

图式15. Fe/HMSI-Box催化卡宾对Si—H键的不对称插入反应

Scheme 15. Fe/HMSI-Box-catalyzed enantioselective insertion of carbenoids into Si—H bonds

图式16. Cu/SpiroBox催化α-重氮芳基乙酸烯丙酯的分子内环丙烷化反应

Scheme 16. Cu/SpiroBox-catalyzed enantioselective cyclopropanation of allyl α-diazo-arylacetates

图式17. 铜或铁催化α-重氮芳基乙酸酯和吲哚的分子内环丙烷化反应

Scheme 17. Cu or Fe-catalyzed enantioselective intramolecular cyclopropanation of α-diazo-arylacetates and indoles

图式18. Pd/SpiroBox催化的联烯不对称串联环化反应

Scheme 18. Pd/SpiroBox-catalyzed enantioselective tandem cyclization reactions

图式19. 基于SPAN骨架的双胺和双亚胺配体及其不对称催化应用

Scheme 19. SPAN-based bis(amine) and bis(imine) ligands and their applications in asymmetric catalysis

图式20. SPANBox的合成及其在铜催化β-酮酸酯的不对称α-羟基化反应

Scheme 20. Synthesis of SPANBox ligands and their applications in Cu-catalyzed asymmetric α-hydroxylation reactions

图式21. SPANBox在锌和铜催化β-酮酸酯的不对称α-氯化反应

Scheme 21. Applications of SPANBox ligands in Zn- and Cu-catalyzed asymmetric α-hydroxylation and α-chlorination reactions

图式22. 螺环四氢吡咯-噁唑啉配体(SPDO)的合成

Scheme 22. Synthesis of spirocyclic pyrrolidine oxazoline (SPDO) ligands

图式23. Cu/SPDO-催化β-萘酚不对称氧化交叉偶联反应

Scheme 23. Cu/SPDO-catalyzed enantioselective oxidative cross-coupling reaction of β-naphthols

图式24. Cu/SPDO-催化β-萘酚交叉偶联反应的可能机理

Scheme 24. Plausible mechanism of Cu/SPDO-catalyzed cross-coupling reaction of β-naphthols

图式25. Cu/SPDO-催化β-萘酚和β-萘酚之间的不对称氧化交叉偶联反应合成BONINs

Scheme 25. Cu/SPDO-catalyzed enantioselective oxidative cross-coupling between β-naphthols and β-naphthylamines for the synthesis of BOBNINs

图式26. Cu(II)/SPDO作为手性Lewis催化酯基取代苯醌的不对称加成反应

Scheme 26. Cu(II)/SPDO as a lewis acid catalyst in enantioselective addition reactions of quinone esters

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