1,n-Rearrangement of allylic alcohols promoted by hot water: application to the synthesis of navenone B, a polyene natural product.
It was reported for the first time that 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. We used the 1,3-rearrangement reaction of an allylic alcohol in hot water as part of an attractive new strategy for construction of the polyene natural product navenone B by iterative use of a Grignard reaction, a 1,3-rearrangement of the resulting allylic alcohol, and subsequent oxidation of the rearranged product.
State Key Laboratory and Institute of Elemento-organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University , Tianjin 300071, China.
Pei-Fang
PF
Li
Heng-Lu
HL
Wang
Jin
J
Qu
D001688:Biological Products / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D011090:Polyenes / Q000138:chemical synthesis* / Q000737:chemistry; D020005:Propanols / Q000737:chemistry*; D014867:Water / Q000737:chemistry*
D001688:Biological Products; D011090:Polyenes; D020005:Propanols; C000593077:navenone B; D014867:Water; C006463:allyl alcohol