Highly Regioselective Sequential 1,1‐Dihydrosilylation of Terminal Aliphatic Alkynes with Primary Silanes

• Published in: Chinese journal of chemistry Vol. 37; no. 5; pp. 457 - 461
• Main Authors: Cheng, Zhaoyang, Xing, Shipei, Guo, Jun, Cheng, Biao, Hu, Lan‐Fang, Zhang, Xing‐Hong, Lu, Zhan
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY‐VCH Verlag GmbH & Co. KGaA 01.05.2019; Wiley; Wiley Subscription Services, Inc
• Subjects: Aliphatic compounds; Alkanes; Alkynes; Bonding; Catalysis; Catalysts; Chemistry; Chemistry, Multidisciplinary; Cobalt; cobalt‐catalyzed; gem‐(bis)silanes; Hydrogen bonding; Hydrogen bonds; Hydrosilylation; Physical Sciences; regioselective; Regioselectivity; Science & Technology; Silanes; Silicon; Substrates; CARBON; ENOL ETHERS; alkynes; cobalt-catalyzed; gem-(bis)silanes; regioselective; CATALYZED ASYMMETRIC HYDROSILYLATION; CROSS-COUPLING REACTIONS; SILICON BOND FORMATION; hydrosilylation; ANTI-MARKOVNIKOV HYDROSILYLATION; GEMINAL BIS(SILANE); SELECTIVE SYNTHESIS; STEREOSELECTIVE HYDROSILYLATION; COBALT
• ISSN: 1001-604X; 1614-7065
• DOI: 10.1002/cjoc.201900079

Summary of main observation and conclusion A regioselective double 1,1‐hydrosilylation of terminal aliphatic alkynes with primary silanes catalyzed by one cobalt catalyst has been developed. gem‐Bis(dihydrosilyl)alkanes containing four silicon‐hydrogen bonds are efficiently constructed in an atom‐economical manner. Tolerated substrates include simplest alkyne‐ethyne, a complicated drug derivative and various functionalized terminal aliphatic alkynes. Asymmetric approach using two catalysts is achieved with excellent enantioselectivities to access corresponding chiral products. The transformations of Si—H bonds into Si—C, Si—O, and Si—F bonds and the synthesis of enantioriched α‐hydroxysilane show synthetic utility.