Proceedings chapter
English

Diastereo- and enantio-selective cycloaddition and ene reactions in organic synthesis

Presented atproceedings of the Fourth International Conference on Organic Synthesis, Tokyo, 22-27 August 1982
Published inNozaki, Hitosi (Ed.), Current trends in organic synthesis, p. 131-149
PublisherOxford : Pergamon Press
Publication date1983
Abstract

1. Highly enantioselective C,C-bond formation has been achieved in a predictable manner

1.1 by Lewis-acid-mediated processes such as intramolecular ene-type reactions (synthesis of (+)-α-allokainic acid), bimolecular Diels-Alder- and 1,4-additions using enoates derived from various chiral alcohols followed by regeneration of the auxiliary group;

1.2 in the "chiral pool"-synthesis of (-)-α-kainic acid from (S)-(-)-glutamic acid via a thermal intramolecular ene reaction, proving the absolute configuration of the neurophysiologically interesting natural products (-)-α-kainic acid, (-)-α-allokainic acid and domoic acid.

2. Intramolecular "magnesium-ene" reactions of 2-alkenylmagnesium chlorides to olefinic bonds have been systematically studied and applied, as illustrated by

2.1 the development of a reliable and efficient preparation of 2-alkenyl Grignard reagents using slurries of evaporated magnesium;

2.2 a synthesis of (±)Δ9,12-capnellene using an iterative cyclopentane-annulation based on type-I-ene reactions;

2.3 a synthesis of the unusual sesquiterpene(±)sinularene via a type-I-reaction;

2.4 regio- and stereochemical studies of unprecedented type II-reactions;

2.5 a direct and highly selective synthesis of the olfactively interesting norsesquiterpene (±)-khusimone exploiting a type-II-reaction.

Citation (ISO format)
VON OPPOLZER, Wolfgang. Diastereo- and enantio-selective cycloaddition and ene reactions in organic synthesis. In: Current trends in organic synthesis. Nozaki, Hitosi (Ed.). Tokyo. Oxford : Pergamon Press, 1983. p. 131–149. doi: 10.1016/b978-0-08-029217-5.50016-4
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