US 9,809,607 B2
Silylation of aromatic heterocycles by earth abundant transition-metal-free catalysts
Anton Toutov, Pasadena, CA (US); Kerry Betz, Boulder, CO (US); Alexey Fedorov, Wallisellen (CH); Brian M. Stoltz, San Marino, CA (US); Wenbo Liu, Pasadena, CA (US); and Robert H. Grubbs, South Pasadena, CA (US)
Assigned to California Institute of Technology, Pasadena, CA (US)
Filed by CALIFORNIA INSTITUTE OF TECHNOLOGY, Pasadena, CA (US)
Filed on Aug. 5, 2015, as Appl. No. 14/818,417.
Prior Publication US 2016/0046653 A1, Feb. 18, 2016
Int. Cl. C08G 75/00 (2006.01); C07F 7/08 (2006.01); C07D 209/12 (2006.01)
CPC C07F 7/0801 (2013.01) [C07D 209/12 (2013.01); C07F 7/0827 (2013.01); C07F 7/0832 (2013.01)] 37 Claims
OG exemplary drawing
 
1. A method comprising contacting an organic substrate comprising an aromatic moiety with a mixture comprising (a) at least one hydrosilane and (b) potassium hydroxide (KOH), under conditions sufficient to silylate the organic substrate, the method resulting in the formation of a silylated organic substrate, wherein the silylated organic substrate has a carbon-silicon bond in a position corresponding to a position on the aromatic moiety having a carbon-hydrogen bond, unless:
(a) the aromatic moiety is an aryl moiety having an alkyl substituent, in which case the silylated organic substrate has a carbon-silicon bond on the carbon alpha to the aryl moiety; or
(b) the aromatic moiety is one having an alkylthioether substituent, in which case the silylated organic substrate has a carbon-silicon bond on the carbon alpha to the thioether sulfur; or
(c) the aromatic moiety is a pyridinyl moiety having alkyl substituents on one or both C2-and C6-positions, in which case the silylated organic substrate has a carbon-silicon bond on the carbon alpha to the pyridinyl ring; or
(d) the aromatic moiety is a heteroaryl moiety comprising a 5-membered heteroaryl ring having no C—H substituents in its C-2 or C-5 position and at least one alkyl substituent in the C-2 or C-5 position, in which case the silylated organic substrate has a carbon-silicon bond on the carbon alpha to the 5-membered heteroaryl ring.