非安定化1,3-双極子反応剤の創製と反応-カルボニルイリドの自在化(Tailor-made)調製法を目指して-

概要

論文の詳細を見る
Unprecedented approach to nonstabilized carbonyl ylides can be attained by the following three methods : 1) the 1, 3-elimination of organosilicon compounds under mild and neutral conditions, 2) the generation from iodomethyl silyl ethers promoted by samarium reagents as a reductant, and 3) the reductive metalation of α-chloroalkyl α -chloroalkyl ethers by samarium and activated manganese reagents followed by 1, 3-elimination of metal halide from the intermediate. The last method is especially attractive for the generation of “<I>Tailor-made</I>” carbonyl ylides bearing not only nonstabilized substituents but also no substituents (the parent carbonyl ylide). Using these novel and synthetically practical carbonyl ylides, it has been elucidated that carbonyl ylides reveals high reactivities toward activated and nonactivated alkenes, alkynes, and a variety of heterodipolarophiles such as compounds including C=O, C=N, C=S, N=N double bonds, and optionally substituted and stereochemically defined tetrahydrofurans, dihydrofurans, dioxolanes, and oxazolidines are conveniently synthesized in a single step.
社団法人有機合成化学協会の論文
1998-08-01