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Synfacts 2014; 10(8): 0848
DOI: 10.1055/s-0034-1378418
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Stereoselective Synthesis of Oxo-Heterocycles via Rhenium Catalysis

Contributor(s):
Hisashi Yamamoto
,
Sukalyan Bhadra
Xie Y, Floreancig PE * University of Pittsburgh, USA
Heterocycle Synthesis Based on Allylic Alcohol Transposition Using Traceless Trapping Groups.

Angew. Chem. Int. Ed. 2014;
53: 4926-4929
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Publication History

Publication Date:
18 July 2014 (online)

 
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Key words

allylic alcohols - isomerization - oxygen heterocycles - rhenium

Significance

Herein, Xie and Floreancig describe a concise synthesis of oxygen-containing heterocycles via a sequence of allylic alcohol transposition, intramolecular trapping, oxocarbenium ion formation and intermolecular nucleophilic addition. In the presence of Re2O7 as catalyst, the ­reaction is initiated by isomerization of the allylic alcohol, which subsequently undergoes ring formation with a terminating agent, for example, Et3SiH.


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Comment

Relative stereocontrol was governed by the transposition, and termination rates and complementary stereoisomers were obtained via reductive and alkylative quenching processes. A high stereocontrol was gained when the rate of transposition is high; that of termination was low. However, the stereocontrol in the tetrahydrofuran formation was lower than that for the tetrahydropyran formation.


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