Diels-Alder dienophiles INDEX

CONTENTS Preface, Mark Lautens. Photocyclization and Phofocycloaddition Reactions of 4- and 2-Pyrones, Frederick G. West. Intramolecular I4+3) Cycloaddition Reactions, Michael Harman. Lewis Acid Catalyzed [2+2] Cycloaddition Reactions of Vinyl Sulfides and Their Analogues Catalytic Asymmetric [2+2] Cycloaddition Reactions, Koichi Narasaka and Yujiro Hayashi. Vinylbo-ranes as Diels-Alder Dienophiles, Daniel A. Singleton. Preparation and Exo-Selective [4+2] Cycloaddition Reactions of Cobaloxime-Substituted 1,3-Dienes, MarkE. Welker, Marcus W. Wright, Heather L. Stokes, B. Matthew Richardson, Torrey A Adams, Terrence L. Smalley, Stacia P. Vaughn, Ginger J. Lohr, Louise Liable-Sands, and Arnold L. Rheingold. Index. 

The hnal copolymer was obtained in 90% yield it had a molecular weight of 10,800 and polydispersity index of 2.1. In this case, Diels-Alder copolymerization dominates over the cyclobntane homopolymerization. It means that Diels-Alder addition of the dienophile cation-radical to the diene is substantially faster than the competing addition of the dienophile cation-radical to the nen-tral dienophile. 

Diazo transfer reactions p-Toluenesulfonyl azide, 226 Diazotization Sodium nitrite, 170, 282 Dicarboxylation (see Addition reactions to carbon-carbon multiple bonds) Diels-Alder reaction (For a list of dienes and dienophiles see Type of Compound Index)... 

The basis of this concept [32] is a simple parallel intuitively felt by Evans [154], between the ease of certain reactions and the arrangement of corresponding transition states. Thus, e.g., the ease of a majority of Diels-Alder reactions is related to the fact that transient structure created by approaching the diene and dienophilic components is isoconjugated, or in other words, topologically equivalent, with the aromatic benzene and as a such should be therefore stabilized, at least in part, as the benzene itself. This simple idea was revived by Dewar [32] who also generalized it into the form of simple rule that (thermally) allowed reactions proceed via aromatic transition states. The proposed theoretical justification of the above criterion arises from a simple idea of direct quantitative evaluation of the resemblance of electron structure of expected transition states with the appropriate aromatic standards. The quantitative measure of this resemblance is the similarily index (102), where Q and ref represent the density matrices of the expected transition state and the appropriate reference standard respectively. 

A tris(4-bromophenyl)ammonium hexachloroantimonate catalyst has been utilized to promote a cation radical mechanism in the Diels-Alder cycloaddition polymerization of a bis(diene) with an ionizable bis(dienophile) (Scheme 2). The polymers were obtained with molecular weights up to ca 10 000 and a polydispersity index of ca 2. The electron-transfer reactions of phenols and its derivatives are also important to the polymer industry for the stabilization of polymers, fats and oils. Pulse radiolysis of naphthols and hydroxybiphenyls in n-butyl chloride at room temperature forms two species-phenol-type radical cations and phenoxyl-type radicals. Two different electron-transfer channels are proposed. The naphthol and hydroxybiphenyl radical cations show increased stability compared with phenol radical cations, presumably due to extensive delocalization over the whole aromatic system. 

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