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Current Organic Synthesis

Editor-in-Chief

ISSN (Print): 1570-1794
ISSN (Online): 1875-6271

α-Activated Cross Conjugated Cycloalkenone Systems in Organic Synthesis

Author(s): Yen-Ku Wu, Tai Wei Ly and Kak-Shan Shia

Volume 7 , Issue 1 , 2010

Page: [78 - 93] Pages: 16

DOI: 10.2174/157017910790820328

Price: $65

Abstract

Under catalysis with an appropriate Lewis acid, the intermolecular Diels-Alder cycloaddition and intramolecular polyene cyclization of the α-activated cross conjugated cycloalkenone systems, possessing particularly increased dienophilicity/electrophilicity in the cross conjugated double bond, proceeded constantly with a high degree of stereochemical control, leading to a variety of synthetically useful molecules, which may serve as advanced intermediates towards many structurally challenging natural products, especially cisclerodane diterpenoids. Mechanistically, an additional conjugated double bond incorporated into the cycloalkenone core of the titled systems might contribute synergistically to the classical secondary orbital effects, thus significantly enhancing the endo-to-ketone addition. In addition, a tandem multiple -bond migration process, an enzymatic pathway prevalent in nature, was proposed to rationalize the formation of structurally unusual polyene-cyclization products occurring under standard chemical conditions.

Keywords: Diels-Alder reaction, cross conjugated, cycloaddition, polyene cyclization, Lewis acids


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