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Silicon‐controlled Carbon–Carbon Bond Formation and Cyclization between Carbonyl Compounds and Allyltrimethylsilane
Author(s) -
Hwu Jih Ru,
Shiao ShuiSheng,
Hakimelahi Gholam H.
Publication year - 1997
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/(sici)1099-0739(199705)11:5<381::aid-aoc592>3.0.co;2-h
Subject(s) - chemistry , cyclopentanes , ceric ammonium nitrate , silylation , manganese(iii) acetate , methylene , acetic acid , medicinal chemistry , organic chemistry , carbon–carbon bond , methanol , silicon , carbon fibers , catalysis , materials science , manganese , composite material , composite number , grafting , polymer
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 · 2H 2 O 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 · 2H 2 O/Cu(OAc) 2 · H 2 O. 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.