HIGHLY STEREOSELECTIVE PREPARATION OF NITRO-OLEFINS AND NITRO-DIENES BY THE ADDITION-ELIMINATION OF COPPER-ZINC ORGANOMETALLICS TO BETA-ALKYLTHIO AND BETA-PHENYLSULFONYL NITRO OLEFINS

[摘要] The addition-elimination of copper-zinc organometallics RCu(CN)ZnX to (E)-1-nitro-2-phenysulfonyl ethylene 2a gave highly functionalized pure (E) nitro olefins and stereoselectively (1E, 3E) and (1E, 3Z)-1-nitrodienes in excellent yields. beta-Alkylthio nitro olefins such as 2-ethylthio-1-nitro-1-cyclohexene 2b and 2,2-dimethylthio-1-nitroethylene 12 were found to have a similar behavior. This methodology allowed an expeditive preparation of the triene 5 which underwent an extremely mild silica gel-catalyzed, stereospecific Diels-Alder cyclization.

[发布日期] 1991-01-21