1-Amino-3-siloxy-1,3-butadienes: Highly Reactive Dienes for the Diels-Alder Reaction

Abstract

1-Amino-3-siloxy-1,3-butadienes represent a novel class of heteroatom-containing dienes with several useful properties. These dienes can be prepared efficiently by deprotonation of readily available vinylogous amides with potassium hexamethylsilazide, followed by silylation of the corresponding potassium enolates. This protocol has been found to be quite general for the preparation of various dienes containing different silyl and amino groups. Amino siloxy dienes readily undergo [4 + 2] cycloadditions with a wide range of electron-deficient dienophiles. The reactions generally occur under very mild conditions to afford the corresponding [4 + 2] adducts in high yields and with complete regioselectivity. High endo selectivity is observed in the case of N-phenylmaleimide and methacrolein. Other cycloadducts are usually obtained as mixtures of endo/exo diastereomers. The cycloadducts are versatile synthetic intermediates. They can be subjected to deprotonation, reduction, and Wittig olefination without any hydrolysis or elimination. In addition, the elimination of the amino group can be cleanly accomplished under acidic conditions leading to the formation of enones. A variety of substituted cyclohexenones can be prepared by this procedure.