Selective Hydrosilylation of Dienes, Enynes, and Diynes Catalyzed by a Platinum Complex with a Very Bulky NHC Ligand – The Crucial Role of Precise Tuning of the Reaction Conditions

Abstract

Series of various dienes, diynes and enynes were hydrosilylated in the presence of platinum complex [Pt(IPr*OMe)(dvms)] (I) (where IPr*OMe=1,3‐bis{2,6‐bis(diphenylmethyl)‐4‐methoxyphenyl}imidazol‐2‐ylidene, dvtms = divinyltetramethyldisiloxane) to afford selectively the corresponding mono‐ and bissilylated products in high yields. In each case, the process proceeded fully regioselectively according to the anti‐Markovnikov rule. Hydrosilylation of carbon–carbon triple bonds led to exclusive formation of E‐isomers. For the first time, a one‐pot sequential hydrosilylation of a selected 1,3‐enyne and symmetric α,ω‐diene with two different silanes was also achieved. Moreover, the optimized reaction conditions were adopted for successful hydrosilylation of 1,3‐enynes with secondary silanes to yield stereoregular polyenes containing terminal carbon–carbon double bonds.