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 language | English (US) |
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Pages (from-to) | 22850-22857 |
Number of pages | 8 |
Journal | Journal of the American Chemical Society |
Volume | 144 |
Issue number | 50 |
DOIs | |
State | Published - 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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CCDC 2181752: Experimental Crystal Structure Determination
Byun, S. (Contributor), Farah, A. O. (Contributor), Wise, H. R. (Contributor), Katchmar, A. (Contributor), Cheong, P.H.-Y. (Contributor) & Scheidt, K. A. (Contributor), Cambridge Crystallographic Data Centre, 2022
DOI: 10.5517/ccdc.csd.cc2c7931, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc2c7931&sid=DataCite
Dataset
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CCDC 2182017: Experimental Crystal Structure Determination
Byun, S. (Contributor), Farah, A. O. (Contributor), Wise, H. R. (Contributor), Katchmar, A. (Contributor), Cheong, P.H.-Y. (Contributor) & Scheidt, K. A. (Contributor), Cambridge Crystallographic Data Centre, 2022
DOI: 10.5517/ccdc.csd.cc2c7knv, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc2c7knv&sid=DataCite
Dataset