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Angew Chem Int Ed Engl. 2018 May 22;57(21):6251-6255. doi: 10.1002/anie.201802963. Epub 2018 Apr 23.

Divergent Control of Point and Axial Stereogenicity: Catalytic Enantioselective C-N Bond-Forming Cross-Coupling and Catalyst-Controlled Atroposelective Cyclodehydration.

Author information

1
Department of Chemistry, Yale University, 225 Prospect Street, New Haven, CT 06520-8107, USA.

Abstract

Catalyst control over reactions that produce multiple stereoisomers is a challenge in synthesis. Control over reactions that involve stereogenic elements remote from one another is particularly uncommon. Additionally, catalytic reactions that address both stereogenic carbon centers and an element of axial chirality are also rare. Reported herein is a catalytic approach to each stereoisomer of a scaffold containing a stereogenic center remote from an axis of chirality. Newly developed peptidyl copper complexes catalyze an unprecedented remote desymmetrization involving enantioselective C-N bond-forming cross-coupling. Then, chiral phosphoric acid catalysts set an axis of chirality through an unprecedented atroposelective cyclodehydration to form a heterocycle with high diastereoselectivity. The application of chiral copper complexes and phosphoric acids provides access to each stereoisomer of a framework with two different elements of stereogenicity.

KEYWORDS:

asymmetric catalysis; atropisomerism; cross-coupling; cyclodehydration; peptides

PMID:
29637680
PMCID:
PMC5964046
DOI:
10.1002/anie.201802963
[Indexed for MEDLINE]
Free PMC Article

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