Hydrosilation of Carbonyl-Containing Substrates Catalyzed by an Electrophilic η-Silane Iridium(III) Complex.

ABSTRACT: Hydrosilation of a variety of ketones and aldehydes using the cationic iridium catalyst, (POCOP)Ir(H)(acetone)(+), 1, (POCOP = 2,6-bis(di-tert-butyl phosphinito)phenyl) is reported. With triethyl silane, all but exceptionally bulky ketones undergo quantitative reactions employing 0.5 mol% catalyst in 20-30 min at 25 °C. Hydrosilation of esters and amides results in over-reduction and cleavage of C-O and C-N bonds, respectively. The diastereoselectivity of hydrosilation of 4-tert-butyl cyclohexanone has been examined using numerous silanes and is highly temperature dependent. Using EtMe(2)SiH, analysis of the ratio of cis:trans hydrosilation products as a function of temperature yields values for ΔΔH(‡) (ΔH(‡) (trans) - ΔH(‡) (cis)) and ΔΔS(‡) (ΔS(‡) (trans) - ΔS(‡)(cis)) of -2.5 kcal/mol a

SUBMITTER: Park S 

PROVIDER: S-EPMC3092162 | biostudies-literature | 2010 Oct

REPOSITORIES: biostudies-literature