Diastereoselective Intramolecular Temporary Silicon-Tethered Rhodium-Catalyzed [4+2+2] Cycloisomerization Reactions:  Regiospecific Incorporation of Substituted 1,3-Butadienes

Transition metal-catalyzed carbocyclization reactions represent powerful methods for the construction of complex polycyclic systems. We have developed a regiospecific and diastereoselective intramolecular temporary silicon-tethered rhodium-catalyzed [4+2+2] cycloisomerization reaction of a tethered...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2004-09, Vol.126 (36), p.11150-11151
Main Authors: Evans, P. Andrew, Baum, Erich W
Format: Article
Language:English
Subjects:
Chemical reactivity
Chemistry
Exact sciences and technology
Organic chemistry
Reactivity and mechanisms
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Summary:Transition metal-catalyzed carbocyclization reactions represent powerful methods for the construction of complex polycyclic systems. We have developed a regiospecific and diastereoselective intramolecular temporary silicon-tethered rhodium-catalyzed [4+2+2] cycloisomerization reaction of a tethered enyne for the construction of tricyclic eight-membered heterocycles and carbocycles. This methodology also allows (E)- and (Z)-olefins to be utilized in a stereospecific manner. The incorporation of either alkene geometry is particularly significant, since related carbocyclization reactions are often limited in this respect. Finally, the ability to utilize carbon-tethered 1,6-enynes and to regiospecifically incorporate substituted 1,3-butadiene derivatives provides exciting opportunities for future applications toward the total synthesis of cyclooctanoid containing diterpenes.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja046030+