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. 2025 Jul 11;27(27):7428-7433.
doi: 10.1021/acs.orglett.5c02258. Epub 2025 Jul 1.

Kinetic Resolution of BINAMs by Stereoselective Copper-Catalyzed Dehydrogenative Si-N Coupling with Prochiral Dihydrosilanes

Finn H Gattwinkel  1 , Martin Oestreich  1
Affiliations

Kinetic Resolution of BINAMs by Stereoselective Copper-Catalyzed Dehydrogenative Si-N Coupling with Prochiral Dihydrosilanes

Finn H Gattwinkel et al. Org Lett. .

Abstract

A nonenzymatic kinetic resolution of monoprotected 1,1'-binaphthyl-2,2'-diamine (BINAM) derivatives is reported. This is achieved by a Cu-H-catalyzed dehydrogenative Si-N coupling with prochiral dihydrosilanes using (R,R)-Ph-BPE as a chiral ligand. The atroposelective as well as diastereoselective N-silylation enables the resolution of BINAMs with various substituents in 6,6'- or 7,7'-positions with good to synthetically useful selectivity factors.

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Figures

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1. Established Approaches for Asymmetric Si–N Coupling, the Kinetic Resolution of BINAMs, and the Planned Merger of Both
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2. Substrate Scope
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3. Stereochemical Control Experiments for the Desymmetrization of the Dihydrosilane
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