摘要/Abstract

在手性分子中，轴手性化合物占据着非常重要的地位.从原子和步骤经济性方面考虑，利用不对称碳-氢官能团化反应构建轴手性化合物是最简洁高效的方法.随着过渡金属催化的不对称碳-氢键官能团化领域的逐步发展，利用该策略来构建轴手性联芳基化合物的研究成果也不断涌现.本文综述了通过过渡金属钯、铑和铱催化的不对称碳-氢键官能团化反应合成轴手性联芳基化合物的最新进展.此外，还介绍了利用这些方法合成多种轴手性配体及其催化的不对称反应，以及这些方法在天然产物合成中的应用.
关键词: 过渡金属催化, 不对称催化, 不对称C-H键官能团化, 轴手性
Axial chirality is of significant importance in chiral molecules. Axially chiral biaryls are existed in numerous natural products and biologically active molecules. Moreover, they have been extensively used as chiral catalysts and chiral ligands in asymmetric catalysis. Due to the importance of these privileged scaffolds, considerable attention has been attracted to develop novel, efficient and practical methods for their asymmetric synthesis by utilizing chiral transition-metal catalysis or chiral organocatalysis. Among those reported elegant achievements, asymmetric C—H bond functionalization reactions are the most concise and efficient methods for the synthesis of axial chiral biaryls in terms of atom and step economies. With the advancement of transition-metal-catalyzed asymmetric C—H bond functionalization reactions, they largely promote the field of asymmetric synthesis of axially chiral biaryls. Recent progress on the development of synthesis of axially chiral biaryls via transition metal (Pd-, Rh-, and Ir-) catalyzed asymmetric C—H bond functionalization reactions are summarized in this review. Those mainly include:Rh-catalyzed enantioselective C(sp²)-H bond alkylation and arylation reactions with the combination of rhodium (I) catalyst precursors and chiral phosphine ligands; Rh-catalyzed enantioselective C(sp²)-H bond alkenylation, arylation and annulation reactions with well-defined chiral rhodium (Ⅲ)-Cp(SCp) complexes; Ir-catalyzed enantioselective C(sp²)-H bond arylation reactions with chiral iridium (Ⅲ)-Cp complex and chiral amino acid as co-catalyst; Pd-catalyzed diastereoselective C(sp²)-H bond alkenylation, iodination, and arylation reactions using chiral p-tolyl sulfoxide auxiliary or menthyl phenylphosphate group as a directing group; Pd-catalyzed intramolecular enantioselective C(sp²)-H bond arylation reaction with Pd(0) catalyst precursors and chiral TADDOL-phosphoramidites; Pd-catalyzed intermolecular enantioselective C(sp²)-H bond iodination, alkenylation, alkynylation, allylation and arylation reactions with Pd(Ⅱ) catalyst precursors and mono-N-protected amino acids (MPAAs). In addition, preparation of varieties of novel axially chiral ligands by utilizing these methods and their applications in catalytic asymmetric reactions are also covered. Meanwhile, applications of these methods as key steps in the synthesis of natural products are also discussed.
Key words: transition metal catalysis, asymmetric catalysis, asymmetric C—H functionalization, axial chirality


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