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<p>Recent developments in chirality chemistry have revealed remarkable instances of atropisomers featuring multiple chiral elements. Despite significant progress in the synthesis and application of atropisomers, developing a synthetic protocol for the simultaneous introduction of axial and point chirality is still a fascinating challenge. In this context, we present a convenient and versatile method for synthesizing novel atropisomers with axial and point chirality. This approach, based on a new reaction mechanism with nickel-controlled Si–C bond activation, facilitates the controllable migratory insertion of aldehydes into the Ni–C bond. We utilize multidimensional strategies of desymmetrization, kinetic resolution and dynamic kinetic resolution to complete enantioselective nickel-catalyzed ring expansion of benzosilacyclobutenes with aldehydes. The design of multidimensional kinetic resolution, desymmetrization, and dynamic resolution, features a straightforward catalytic system, mild reaction conditions, and broad functional group tolerances. Various axially chiral biaryl oxasilacycles bearing carbon- or silicon-stereogenic centers are obtained with excellent diastereo- and enantio-selectivities (up to &gt;20:1 <i>dr</i> and &gt;99.9% <i>ee</i>) through the use of a chiral Ni complex with a large cavity-type 1,1,4,4-tetra-aryl-2,3-<i>O</i>-isopropylidene-<i>L</i>-threitol (TADDOL)-derived phosphoramidite ligand.</p>

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Construction of axial and point chirality through Ni-catalyzed sila-cycloaddition reaction via desymmetrization and (dynamic) kinetic resolution

  • 期刊论文

  • 发表日期：

    2025年2月6日

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  • Hua-Jie Zhu,
  • Ming-Hao Shen,
  • Jia-Wei Si,
  • Wei-Ke Zhu,
  • Xiao-Jun Fang,
  • Fei Ye,
  • Jian Cao,
  • Zheng Xu,
  • Li-Wen Xu

摘要

Recent developments in chirality chemistry have revealed remarkable instances of atropisomers featuring multiple chiral elements. Despite significant progress in the synthesis and application of atropisomers, developing a synthetic protocol for the simultaneous introduction of axial and point chirality is still a fascinating challenge. In this context, we present a convenient and versatile method for synthesizing novel atropisomers with axial and point chirality. This approach, based on a new reaction mechanism with nickel-controlled Si–C bond activation, facilitates the controllable migratory insertion of aldehydes into the Ni–C bond. We utilize multidimensional strategies of desymmetrization, kinetic resolution and dynamic kinetic resolution to complete enantioselective nickel-catalyzed ring expansion of benzosilacyclobutenes with aldehydes. The design of multidimensional kinetic resolution, desymmetrization, and dynamic resolution, features a straightforward catalytic system, mild reaction conditions, and broad functional group tolerances. Various axially chiral biaryl oxasilacycles bearing carbon- or silicon-stereogenic centers are obtained with excellent diastereo- and enantio-selectivities (up to >20:1 dr and >99.9% ee) through the use of a chiral Ni complex with a large cavity-type 1,1,4,4-tetra-aryl-2,3-O-isopropylidene-L-threitol (TADDOL)-derived phosphoramidite ligand.