Enantioselective Copper-Catalyzed Borylative Amidation of Allenes

Seunghwan Byun, Abdikani Omar Farah, Henry R. Wise, Andrew Katchmar, Paul H.Y. Cheong*, Karl A. Scheidt*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

25 Scopus citations

Abstract

An approach for the copper-catalyzed synthesis of enantioenriched amides bearing an α-stereogenic center is disclosed. This method involves the addition of an allyl copper species to an isocyanate and allows access to α-substituted chiral amides in high yields and high-to-excellent enantioselectivities. The utility of α-vinyl β-boryl amides in synthesis is highlighted by the diversification of products to afford highly useful scaffolds. DFT calculations reveal that the catalyst preferentially coordinates to the oxygen of the isocyanate. Enantiocontrol arises from the steric repulsion between the boryl group and the stereodirecting phenyl of the chiral ligand.

Original languageEnglish (US)
Pages (from-to)22850-22857
Number of pages8
JournalJournal of the American Chemical Society
Volume144
Issue number50
DOIs
StatePublished - Dec 21 2022

Funding

This work is dedicated to the memory of Professor David A. Evans (1941–2022), a supremely talented scientist and remarkable mentor. We thank the NSF (CHE-1665141, CHE-2154820) and Northwestern University for financial support of this work. A.K. thanks Northwestern for a summer undergraduate research grant. PHYC is the Bert and Emelyn Christensen professor of OSU, and gratefully acknowledges financial support from the Vicki & Patrick F. Stone family and the computing infrastructure in part provided by the NSF Phase-2 CCI, Center for Sustainable Materials Chemistry (NSF CHE-1102637). We thank Dr. Anna Bay for her comments and assistance with the preparation of this manuscript. We thank Charlotte Stern and Cullen Schull for X-ray crystallographic assistance as well as Dr. Ada Kwong and Dalton Kim for assistance with HRMS.

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry

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