om9603979_si_001.pdf (1.28 MB)
[Ru((R)-2,2‘-bis(diphenylphosphino)-1,1‘-binaphthyl)(H)(MeCN)(THF)2](BF4), a Catalyst System for Hydrosilylation of Ketones and for Isomerization, Intramolecular Hydrosilylation, and Hydrogenation of Olefins
journal contributionposted on 1996-09-03, 00:00 authored by Jason A. Wiles, Christopher E. Lee, Robert McDonald, Steven H. Bergens
(R)-2,2‘-Bis(diphenylphosphino)-1,1‘-binaphthyl ((R)-BINAP) reacted with cis-[Ru(MeCN)2(COD)(η3-C3H5)](BF4) (COD = cycloocta-1,5-diene) to generate two isomers of [Ru(MeCN)((R)-BINAP)((1−3-η):(5,6-η)-C8H11)](BF4) (1) that reacted with an excess of dihydrogen gas (pressure H2 ∼1 atm, ambient temperature) in THF and methylene chloride (∼5:1) to generate [Ru((R)-BINAP)(H)(MeCN)(THF)2](BF4) (2). Reactions effected using 2 mol % 2 as catalyst include hydrogenation of (Z)-methyl α-acetamidocinnamate, hydrosilylation of ethyl acetoacetate by chlorodimethylsilane, tandem, stereoselective isomerization of (rac)-3-buten-2-ol via a partial kinetic resolution (ee of 3-buten-2-ol 42% S at 50% conversion) to initially generate (Z)-2-buten-2-ol, followed by isomerization of the enol to 2-butanone, and competing isomerization and intramolecular hydrosilylation of dimethyl(2-propen-1-oxy)silane.