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J Am Chem Soc. 2017 Dec 13;139(49):18107-18114. doi: 10.1021/jacs.7b11197. Epub 2017 Nov 27.

Enantioselective Intermolecular C-O Bond Formation in the Desymmetrization of Diarylmethines Employing a Guanidinylated Peptide-Based Catalyst.

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1
Department of Chemistry, Yale University , P.O. Box 208107, New Haven, Connecticut 06520-8107, United States.

Abstract

We report a series of enantioselective C-O bond cross-coupling reactions based on remote symmetry breaking processes in diarylmethine substrates. The key to the chemistry is multifunctional guanidinylated peptide-based ligands that allow highly selective, intermolecular Cu-catalyzed cross-coupling of phenolic nucleophiles. The scope of the process is explored, demonstrating efficiency for substrates with a range of electronic and steric perturbations to the nucleophile. Scope and limitations are also reported for variation of the diarylmethine. While the presence of an intervening tBu group is found to be optimal for maximum enantioselectivity, several other substituents may also be present such that appreciable selectivity can be achieved, providing an uncommon level of scope for diarylmethine desymmetrizations. In addition, chemoselective reactions are possible when there are phenolic hydroxyl groups within substrates that contain a second reactive site, setting the stage for applications in diverse complex molecular settings.

PMID:
29116792
PMCID:
PMC5738244
DOI:
10.1021/jacs.7b11197
[Indexed for MEDLINE]
Free PMC Article

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