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J Am Chem Soc. 2016 Jun 29;138(25):7939-45. doi: 10.1021/jacs.6b03444. Epub 2016 Jun 15.

Distal Stereocontrol Using Guanidinylated Peptides as Multifunctional Ligands: Desymmetrization of Diarylmethanes via Ullman Cross-Coupling.

Author information

1
Department of Chemistry, Yale University , New Haven, Connecticut 06520-8107, United States.
2
Chemical Development, Boehringer Ingelheim Pharmaceuticals, Inc. , 900 Ridgebury Road, P.O. Box 368, Ridgefield, Connecticut 06877-0368, United States.
3
Chemical Research and Development, Pfizer Inc. , Eastern Point Road, Groton, Connecticut 06340, United States.

Abstract

We report the development of a new class of guanidine-containing peptides as multifunctional ligands for transition-metal catalysis and its application in the remote desymmetrization of diarylmethanes via copper-catalyzed Ullman cross-coupling. Through design of these peptides, high levels of enantioinduction and good isolated yields were achieved in the long-range asymmetric cross-coupling (up to 93:7 er and 76% yield) between aryl bromides and malonates. Our mechanistic studies suggest that distal stereocontrol is achieved through a Cs-bridged interaction between the Lewis-basic C-terminal carboxylate of the peptides with the distal arene of the substrate.

PMID:
27254785
PMCID:
PMC5127171
DOI:
10.1021/jacs.6b03444
[Indexed for MEDLINE]
Free PMC Article

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