Regioselective Reversal in the Cyclization of 2-Diazo-3,5-dioxo-6-ynoates (Ynones, Ynamide): Construction of γ-Pyrones and 3(2H)-Furanones Starting from Identical Materials

Feng Wang; Shengle Lu; Bo Chen; Yali Zhou; Ying Yang; Guisheng Deng

doi:10.1021/acs.orglett.6b02973

Regioselective Reversal in the Cyclization of 2-Diazo-3,5-dioxo-6-ynoates (Ynones, Ynamide): Construction of γ-Pyrones and 3(2H)-Furanones Starting from Identical Materials

Org Lett. 2016 Dec 16;18(24):6248-6251. doi: 10.1021/acs.orglett.6b02973. Epub 2016 Dec 5.

Authors

Feng Wang^{1

2}, Shengle Lu^{1

2}, Bo Chen^{1

2}, Yali Zhou^{1

2}, Ying Yang^{1

2}, Guisheng Deng^{1

2}

Affiliations

¹ Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China), Hunan Normal University , Changsha 410081, China.
² Key Laboratory of the Assembly and Application of Organic Functional Molecules, Hunan Normal University , Changsha 410081, China.

PMID: 27978667
DOI: 10.1021/acs.orglett.6b02973

Abstract

The AgSbF₆-catalyzed cyclization of 2-diazo-3,5-dioxo-6-ynoates (ynones, ynamide) in alcoholic solvents affords γ-pyrones, whereas the AgOAc-catalyzed cyclization in 1,2-dichloroethane (DCE) produces 3(2H)-furanones. The cyclization reactions proceeded cleanly under mild reaction conditions, and the desired γ-pyrones or 3(2H)-furanones were obtained in excellent yield. It was observed for the first time that both the catalyst and solvent play key roles in the selective formation. This unique method for the reversal of regioselectivity proved to be highly efficient except for substrates with aliphatic and Me₃Si groups at the triple bond position.

Publication types

Research Support, Non-U.S. Gov't