Work

Stereoselective Construction of Cyclic Ethers Using a Tandem Two-Component Etherification: Elucidation of the Role of Bismuth Tribromide

Year: 2003

Type: article

Abstract: The stereodivergent construction of cyclic ethers remains an important area of synthetic interest, particularly given the ubiquity of C-glycoside derivatives in natural and unnatural pharmacologically important agents. This work describes a series of intramolecular etherification reactions of delta-trialkylsilyloxy aldehydes and ketones using catalytic bismuth tribromide and various trialkylsilyl nucleophiles for the construction of cis- and trans-2,6-di- and trisubstituted tetrahydropyrans. Furthermore, this study provides compelling evidence for the fact that the catalysis may be attributed to the hydrogen bromide and bismuth oxybromide derived from the hydrolysis of bismuth tribromide. The synthetic utility of this protocol is highlighted in the ability to construct adjacent tertiary ethers in a highly stereoselective manner and the development of a sequential two-component cross-coupling followed by reductive etherification process for the expeditious synthesis of nonadjacent tetrahydropyran rings.

Source: Journal of the American Chemical Society

DOI: 10.1021/ja036439j

Authors: P. Andrew Evans, Jian Cui, Santosh J. Gharpure, Robert J. Hinkle

Institutions: Indiana University Bloomington, Indiana University

Language: English

Topic: Organic Chemistry Synthesis Methods

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: National Institutes of Health, National Institute of General Medical Sciences

Awards: G3292294395, G3864295906, Stereoselective Synthesis of Cyclic Ethers, New Rhodium-Catalyzed Allylic Alkylation Reactions