Stereoselectivity of diene-transmissive diels-alder reaction; cycloaddition reaction of cross-conjugated triene system to olefinic dienophiles
05 Oct 1983-Chemistry Letters (The Chemical Society of Japan 公益社団法人 日本化学会)-Vol. 12, Iss: 10, pp 1525-1528
TL;DR: In this article, the steric regulation of diene-transmissive Diels-Alder reaction with olefinic dienophiles has been investigated and the stereoselectivity of 3-benzylidene, 2-4-bis(trimethylsilyloxy)-1,4-pentadiene, with a variety of ODEs was investigated.
Abstract: The stereoselectivity of diene-transmissive Diels–Alder reaction of a cross-conjugated triene, 3-benzylidene-2,4-bis(trimethylsilyloxy)-1,4-pentadiene, with a variety of olefinic dienophiles was investigated. Cyclic dienophiles gave the stereoselective bis-adducts via the endo mono-cycloadducts, whereas the exo mono-adducts were obtained as major products in the reaction with acyclic dienophiles. The steric regulation of diene-transmissive Diels–Alder reaction was discussed.
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TL;DR: In this paper, a line of distinction between the mechanistic alternatives for the Diels-Alder reaction was drawn, considering all experimental and theoretical criteria, for one-step and two-step reactions.
Abstract: The question of concerted or consecutive bond formation arises in all types of cycloaddition reactions. Stereochemical investigations and studies of regiospecificity as well as intensive kinetic investigations with regard to substituent and solvent effects, and the dependence of the reaction on temperature and pressure permit in many cases mechanistic conclusions concerning the Diels-Alder reaction. Efforts towards a theoretical interpretation, ab initio and semiempirical calculations, the application of frontier molecular orbital theory (FMO) as well as thermochemical measurements permit a description of the energy hypersurface of these [4+2]-cycloadditions. An attempt is made here to draw a line of distinction between the mechanistic alternatives—one-step reaction versus two-step reaction—considering all experimental and theoretical criteria.
827 citations
TL;DR: The possible mechanisms of the preparatively so productive Diels-Alder reactions are discussed critically on the basis of experimental data as discussed by the authors, although most of the facts can be explained readily by a synchronous mechanism, a number of problems remains.
Abstract: The possible mechanisms of the preparatively so productive Diels-Alder reactions are discussed critically on the basis of experimental data. Although most of the facts can be explained readily by a synchronous mechanism, a number of problems remains.
421 citations
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