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1,n-Rearrangement of Allylic Alcohols Promoted by Hot Water: Application to the Synthesis of Navenone B, a Polyene Natural Product

Pei-Fang Li, Heng-Lu Wang and Jin Qu*

*State Key Laboratory and Institute of Elemento-organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071, China, Email:

P.-F. Li, H.-L. Wang, J. Qu, J. Org. Chem., 2014, 79, 3955-3962.

DOI: 10.1021/jo5004086

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Hot water as a mildly acidic catalyst efficiently promoted 1,n-rearrangement (n = 3, 5, 7, 9) of allylic alcohols. In some cases, the rearrangement reactions joined isolated C-C double or triple bonds to generate conjugated polyene or enyne structure motifs. The polyene natural product navenone B has been constructed by iterative use of a Grignard reaction, a 1,3-rearrangement of the resulting allylic alcohol, and subsequent oxidation.

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Key Words

allylic alcohols, isomerisations, enynes, dienes

ID: J42-Y2014