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Cyclic(Alkyl)(Amino)Carbene Ligands Enable Cu-Catalyzed Markovnikov Protoboration and Protosilylation of Terminal Alkynes: A Versatile Portal to Functionalized Alkenes

preprint
submitted on 12.04.2021, 22:49 and posted on 13.04.2021, 13:14 by Yang Gao, Sima Yazdani, Aaron Kendrick, Glen Junor, Douglas Grotjahn, Guy Bertrand, Rodolphe Jazzar, Keary Engle
Regioselective hydrofunctionalization of alkynes represents a straightforward route to access alkenyl boronate and silane building blocks. In previously reported catalytic systems, high selectivity is achieved with a limited scope of substrates and/or reagents, with general solutions lacking. Herein, we describe a selective copper-catalyzed Markovnikov hydrofunctionalization of terminal alkynes that is facilitated by strongly donating cyclic (alkyl)(amino)carbene (CAAC) ligands. Using this method, both alkyl- and aryl-substituted alkynes are coupled with a variety of boryl and silyl reagents with high α-selectivity. The reaction is scalable, and the products are versatile intermediates that can participate in various downstream transformations. Preliminary mechanistic experiments shed light on the role of CAAC ligands in this process.

Funding

NIH 5R35GM125052-04

NIH 5R35GM125052-04S1

ACS PRF Doctoral New Investigator Grant

DOE BES DE-SC0009376

NSF CHE-1800598

NSF DGE-1650112

Agence Nationale de la Recherche ANR-19-276 CE07-0017

History

Email Address of Submitting Author

keary@scripps.edu

Institution

The Scripps Research Institute

Country

United States

ORCID For Submitting Author

0000-0003-2767-6556

Declaration of Conflict of Interest

No conflict of interest to declare.

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