Transient-axial-chirality controlled asymmetric rhodium-carbene C(sp2)-H functionalization for the synthesis of chiral fluorenes

Kuiyong Dong, Xing Fan, Chao Pei, Yang Zheng, Sailan Chang, Ju Cai, Lihua Qiu, Zhi-Xiang Yu () and Xinfang Xu ()
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Kuiyong Dong: School of Pharmaceutical Sciences, Sun Yat-sen University
Xing Fan: Peking University
Chao Pei: Soochow University
Yang Zheng: Soochow University
Sailan Chang: Soochow University
Ju Cai: Soochow University
Lihua Qiu: Soochow University
Zhi-Xiang Yu: Peking University
Xinfang Xu: School of Pharmaceutical Sciences, Sun Yat-sen University

Nature Communications, 2020, vol. 11, issue 1, 1-10

Abstract: Abstract In catalytic asymmetric reactions, the formation of chiral molecules generally relies on a direct chirality transfer (point or axial chirality) from a chiral catalyst to products in the stereo-determining step. Herein, we disclose a transient-axial-chirality transfer strategy to achieve asymmetric reaction. This method relies on transferring point chirality from the catalyst to a dirhodium carbene intermediate with axial chirality, namely a transient-axial-chirality since this species is an intermediate of the reaction. The transient chirality is then transferred to the final product by C(sp2)-H functionalization reaction with exceptionally high enantioselectivity. We also generalize this strategy for the asymmetric cascade reaction involving dual carbene/alkyne metathesis (CAM), a transition-metal-catalyzed method to access chiral 9-aryl fluorene frameworks in high yields with up to 99% ee. Detailed DFT calculations shed light on the mode of the transient-axial-chirality transfer and the detailed mechanism of the CAM reaction.

Date: 2020
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DOI: 10.1038/s41467-020-16098-8

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