Cobalt‐Catalyzed Regio‐, Diastereo‐ and Enantioselective Intermolecular Hydrosilylation of 1,3‐Dienes with Prochiral Silanes

• Published in: Angewandte Chemie Vol. 134; no. 30
• Main Authors: Wang, Lei, Lu, Wenxin, Zhang, Jiwu, Chong, Qinglei, Meng, Fanke
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 25.07.2022
• Subjects: 1,3-Dienes; Carbon; Chemistry; Cobalt; Construction; Dienes; Enantiomers; Enantioselective Catalysis; Hydrosilylation; Silanes; Silicon; Silicon-Stereogenic Center; Stereoselectivity
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.202205624

One of the most straightforward approaches to access chiral silanes is catalytic enantioselective hydrosilylation. Although significant advances have been achieved in enantioselective construction of either a carbon‐stereogenic center or a silicon‐stereogenic center through enantioselective hydrosilylation, simultaneous establishment of a carbon‐ and a silicon‐stereogenic center in an acyclic molecule through a single intermolecular hydrosilylation remained undeveloped. Herein, an unprecedented cobalt‐catalyzed regio‐, diastereo‐ and enantioselective hydrosilylation of 1,3‐dienes is presented, enabling construction of a carbon‐ and a silicon‐stereogenic center in a single intermolecular transformation. A wide range of chiral silanes bearing a carbon‐ and a silicon‐stereogenic center were generated in high efficiency and stereoselectivity. Functionalization of the enantioenriched silanes delivered a variety of valuable chiral building blocks that are otherwise difficult to access. A new approach for highly regio‐, diastereo‐ and enantioselective intermolecular hydrosilylation of 1,3‐dienes promoted by an easily accessible Co complex to afford a wide range of enantioenriched acyclic silanes was developed. This protocol represents the first intermolecular example of simultaneous construction of a C‐ and a Si‐stereogenic center through metal‐catalyzed hydrosilylation.