ISSN:
0268-2605
Keywords:
silicon-controlled
;
bond formation
;
cyclization
;
allyltrimethylsilane
;
1,3-diketones
;
β-ketoesters
;
malonates
;
ceric ammonium nitrate
;
manganese(III) acetate
;
Chemistry
;
Industrial Chemistry and Chemical Engineering
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The effect of silicon on C-C bond formation between carbonyl compounds and allyltrimethylsilane was investigated. Treatment of 1,3-diketones, β-ketoesters or malonates with allyltrimethylsilane in the presence of ceric ammonium nitrate (CAN) in methanol produced the corresponding allylated products. Furthermore, introduction of Mn(OAc)3 · 2H2O into those reactions for replacement or assistance of CAN afforded silicon-containing cyclopentanes in 51-75% yields. A sequential process involving allylation, free-radical cyclization and elimination was also developed by use of CAN/Mn (OAc)3 · 2H2O/Cu(OAc)2 · H2O. Accordingly, β-ketoesters or malonates were allowed to react with allylsilanes in acetic acid to give silicon-containing cyclopentanes with an exo methylene unit in 52-71% yields. These reactions involved carbocationic and carboradical intermediates, of which formation and chemical activities were controlled by a β-silyl group. © 1997 by John Wiley & Sons, Ltd.
Additional Material:
4 Tab.
Type of Medium:
Electronic Resource
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