Citation: Wang Qiaotian, Han Caifang, Feng Xiangqing, Du Haifeng. Chiral Spiro Dienes Derived Boranes for Asymmetric Hydrosilylation of Ketones[J]. Chinese Journal of Organic Chemistry, ;2019, 39(8): 2257-2263. doi: 10.6023/cjoc201903076 shu

Chiral Spiro Dienes Derived Boranes for Asymmetric Hydrosilylation of Ketones

Wang Qiaotian ^a,b ,
Han Caifang ^a,b ,
Feng Xiangqing ^a,b,, ,
Du Haifeng ^a,b,,

a.
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190
b.
University of Chinese Academy of Sciences, Beijing 100049

Corresponding author: Feng Xiangqing, fxq@iccas.ac.cn Du Haifeng, haifengdu@iccas.ac.cn
Received Date: 30 March 2019
Revised Date: 24 April 2019
Available Online: 10 August 2019
Fund Project: the National Natural Science Foundation of China 21825108Project supported by the National Natural Science Foundation of China (No. 21825108)

Figures(5)

The chemistry of frustrated Lewis pairs (FLPs) is among the challenging frontiers of synthetic chemistry, which provides a powerful approach for metal-free catalytic hyrogenations and Piers-type hydrosilylations. In recent years, a significant progress has been made in this field. However, the deveopment of asymmetric reactions is still sluggish. The lacks of highly effective and enantioselective chiral FLP catalysts represent the key issue. C₂-symmetric 1, 1'-spirobiindane is one privileged framework in chiral ligands and catalysts. On the basis of chiral binaphthyl diene-derived frustrated Lewis pairs (FLPs) developed by our group, in this work, we designed and synthesized a novel class of chiral spiro dienes, which could further react with Piers' borane via the hydroboration reaction to generate chiral boranes in situ. With the combination of chiral borane and tri-tert-butylphosphine as an FLP catalyst, an asymmetric Piers-type hydrosilylation of simple ketones was successfully realized to give the desired secondary alcohols with up to 90% ee.
- asymmetric catalysis,
- asymmetric hydrosilylation,
- frustrated Lewis pairs,
- chiral spiro dienes,
- ketones
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