Copper-catalyzed enantioselective Sonogashira-type oxidative cross-coupling of unactivated C(sp3)−H bonds with alkynes

Zhen-Hua Zhang, Xiao-Yang Dong, Xuan-Yi Du, Qiang-Shuai Gu, Zhong-Liang Li and Xin-Yuan Liu ()
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Zhen-Hua Zhang: Linyi University
Xiao-Yang Dong: Southern University of Science and Technology
Xuan-Yi Du: Southern University of Science and Technology
Qiang-Shuai Gu: Southern University of Science and Technology
Zhong-Liang Li: Southern University of Science and Technology
Xin-Yuan Liu: Southern University of Science and Technology

Nature Communications, 2019, vol. 10, issue 1, 1-10

Abstract: Abstract Transition metal-catalyzed enantioselective Sonogashira-type oxidative C(sp3)—C(sp) coupling of unactivated C(sp3)−H bonds with terminal alkynes has remained a prominent challenge. The difficulties mainly stem from the regiocontrol in unactivated C(sp3)—H bond functionalization and the inhibition of readily occurring Glaser homocoupling of terminal alkynes. Here, we report a copper/chiral cinchona alkaloid-based N,N,P-ligand catalyst for asymmetric oxidative cross-coupling of unactivated C(sp3)—H bonds with terminal alkynes in a highly regio-, chemo-, and enantioselective manner. The use of N-fluoroamide as a mild oxidant is essential to site-selectively generate alkyl radical species while efficiently avoiding Glaser homocoupling. This reaction accommodates a range of (hetero)aryl and alkyl alkynes; (hetero)benzylic and propargylic C(sp3)−H bonds are all applicable. This process allows expedient access to chiral alkynyl amides/aldehydes. More importantly, it also provides a versatile tool for the construction of chiral C(sp3)—C(sp), C(sp3)—C(sp2), and C(sp3)—C(sp3) bonds when allied with follow-up transformations.

Date: 2019
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DOI: 10.1038/s41467-019-13705-1

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