Enantioselective construction of six- and seven-membered triorgano-substituted silicon-stereogenic heterocycles

Shuyou Chen,Pei-Lin Mai,Yingzi Li,Delong Mu,Chuan He,Jie Ke

doi:10.1038/s41467-021-21489-6

Shuyou Chen, Pei-Lin Mai + Show 4 more

Open Access

https://doi.org/10.1038/s41467-021-21489-6

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Abstract

The exploitation of chirality at silicon in asymmetric catalysis is one of the most intriguing and challenging tasks in synthetic chemistry. In particular, construction of enantioenriched mediem-sized silicon-stereogenic heterocycles is highly attractive, given the increasing demand for the synthesis of novel functional-materials-oriented silicon-bridged compounds. Here, we report a rhodium-catalyzed enantioselective construction of six- and seven-membered triorgano-substituted silicon-stereogenic heterocycles. This process undergoes a direct dehydrogenative C−H silylation, giving access to a wide range of triorgano-substituted silicon-stereogenic heterocycles in good to excellent yields and enantioselectivities, that significantly enlarge the chemical space of the silicon-centered chiral molecules. Further elaboration of the chiral monohydrosilane product delivers various corresponding tetraorgano-substituted silicon-stereogenic heterocycles without the loss of enantiopurity. These silicon-bridged heterocycles exhibit bright blue fluorescence, which would have potential application prospects in organic optoelectronic materials.

Highlights

The exploitation of chirality at silicon in asymmetric catalysis is one of the most intriguing and challenging tasks in synthetic chemistry
To the best of our knowledge, only Shintani, Hayashi, Nozaki et al and Song have succeeded in forming six-membered tetraorgano-substituted siliconstereogenic silanes (Fig. 1b)39–43, while the construction of Sichirality on six- and seven-membered triorgano-substituted monohydrosilanes via asymmetric catalysis is still unknown to date, which is presumably due to a lack of general and efficient synthetic methods
Given the increasing demand for the synthesis of novel functional-materials-oriented silicon-bridged biaryls, construction of six- or seven-membered monohydrosilanes in a chiral version is highly attractive. These interesting chiral monohydrosilane heterocycles may find various synthetic applications in stereospecific transformations[44,45,46,47,48,49], which could lead to their potential applications in new chiral organic materials

Summary

Introduction

The exploitation of chirality at silicon in asymmetric catalysis is one of the most intriguing and challenging tasks in synthetic chemistry. To the best of our knowledge, only Shintani, Hayashi, Nozaki et al and Song have succeeded in forming six-membered tetraorgano-substituted siliconstereogenic silanes (Fig. 1b)39–43, while the construction of Sichirality on six- and seven-membered triorgano-substituted monohydrosilanes via asymmetric catalysis is still unknown to date, which is presumably due to a lack of general and efficient synthetic methods.

Results

Conclusion