Enantioselective Hydrosilylation of β,β‐Disubstituted Enamides to Construct α‐Aminosilanes with Vicinal Stereocenters

• Published in: Angewandte Chemie International Edition Vol. 62; no. 1; pp. e202214534 - n/a
• Main Authors: Zhang, Wen‐Wen, Li, Bi‐Jie
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 02.01.2023; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Alkene Hydrofunctionalization; Alkenes; Chemistry; Chemistry, Multidisciplinary; Enantiomers; Hydrosilylation; Physical Sciences; Rhodium; Rhodium Catalysis; Science & Technology; Stereoisomerism; Stereoisomers; Substrate Directed Reaction; Substrates; α-Aminosilane; Substrate Directed Reaction; alpha-Aminosilane; N-HETEROCYCLIC CARBENE; HYDROGENATION; TRANSITION-METAL-COMPLEXES; Hydrosilylation; Alkene Hydrofunctionalization; SILYLATION; CATALYZED ASYMMETRIC HYDROSILYLATION; Rhodium Catalysis; STEREOSELECTIVE-SYNTHESIS; INHIBITORS; NUCLEOPHILIC SILICON; BOND; SILYLAMINES; α-Aminosilane
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202214534

Despite the advances in the area of catalytic alkene hydrosilylation, the enantioselective hydrosilylation of alkenes bearing a heteroatom substituent is scarce. Here we report a rhodium‐catalyzed hydrosilylation of β,β‐disubstituted enamides to directly afford valuable α‐aminosilanes in a highly regio‐, diastereo‐, and enantioselective manner. Stereodivergent synthesis could be achieved by regulating substrate geometry and ligand configuration to generate all the possible stereoisomers in high enantio‐purity. A rhodium complex bearing a chiral phosphite ligand catalyzes the hydrosilylation of β,β‐disubstituted enamides to afford valuable α‐aminosilanes in a highly regio‐, diastereo‐, and enantioselective manner. Stereodivergent synthesis is achieved by regulating substrate geometry and ligand enantiomer to generate all the possible stereoisomers in high enantio‐purity.