ISSN:
0009-2940
Keywords:
Michael addition of Si groups
;
Cuprates, higher-order
;
Ketones, β-aryl β-silyl
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Direct Michael-Type Addition of Si-Groups to α,β-Unsaturated p-Aryl-Substituted Enones with R3SiCl/Bu2Cu(CN)Li2(E)-5-Benzylidene-2-tert-butyl-6-methyl-1,3-dioxan-4-one (1) undergoes conjugative silylation (Me3Si, Et3Si, tBuMe2Si, Me2PhSi, products 2 - 5) with the reagent specified in the title. The reaction is highly diastereoselective, with formal anti addition of R3Si and H from the Re- and Si-face, respectively, of the exocyclic double bond [proof by NMR analysis and chemical correlation (cf. 6 and 7). A screening of various enone systems showed that this unprecedented Michael addition of Si groups with chlorosilane as a reagent, and under non-reducing conditions occurs only if the x,p-unsaturated carbonyl system bears an aryl group in the P-position to give β-aryl β-silyl ketones (products 8- 15).
Additional Material:
1 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19901231227
