Reactions of 1-tosyl-3-substituted indoles with conjugated dienes under thermal and/or high-pressure conditions.

Abstract

The behavior of 1-tosyl-3-acetylindole (1a), N,N-diethyl-1-tosyl-3-indoleglyoxylamide (1b), and 1-tosyl-3-nitroindole (1c) as dienophiles in Diels-Alder reactions under thermal and/or high-pressure conditions was explored with different dienes: isoprene (2), 1-(N-acetyl-N-propylamino)-1,3-butadiene (3), and 1-methoxy-3-trimethylsilyloxy-1,3-butadiene (Danishefsky's diene) (4). Compared to the acylated indoles, the nitro derivative proved to be the best dienophile. In general, the use of Danishefsky's diene led to high-yielding reactions under milder conditions. Likewise, high-pressure conditions proved to be better in producing high yields of products. The advantage of high-pressure over thermal conditions was the ability of the former to generate highly functionalized adducts in better yields, which were otherwise very difficult or impossible to obtain. The use of thermal or high-pressure conditions led to different regio- and/or stereoselectivity in the adducts, allowing control of the regio- or stereoisomer produced.