title: A Novel Allyl Transfer Coupled with a Grob Fragmentation.
abstract: A novel acid-promoted rearrangement is disclosed. In the previously unknown transformation, an allyl group migrated to an in situ formed carbocation stabilized by an electron-rich aryl or heteroaryl group, resulting in a stereoselective intramolecular Grob fragmentation. The outcome of the rearrangement observed with an array of substrates can be satisfactorily rationalized using a working hypothesis with the aid of a six-membered transition state similar to those proposed for the anionic oxy-Cope or oxonia-Cope rearrangements, but involving only one instead of two double bonds.
authors: State Key Laboratory of Bioorganic and Natural Products Chemistry, Collaborative Innovation Center of Chemistry for Life Sciences, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.
authors: Shao-Gang
authors: SG
authors: Li
authors: State Key Laboratory of Bioorganic and Natural Products Chemistry, Collaborative Innovation Center of Chemistry for Life Sciences, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.
authors: Hui-Jun
authors: HJ
authors: Chen
authors: State Key Laboratory of Bioorganic and Natural Products Chemistry, Collaborative Innovation Center of Chemistry for Life Sciences, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.
authors: Yang-Yang
authors: YY
authors: Yang
authors: State Key Laboratory of Bioorganic and Natural Products Chemistry, Collaborative Innovation Center of Chemistry for Life Sciences, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.
authors: Wen-Ju
authors: WJ
authors: Wu
authors: State Key Laboratory of Bioorganic and Natural Products Chemistry, Collaborative Innovation Center of Chemistry for Life Sciences, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China. yikangwu@sioc.ac.cn.
authors: Yikang
authors: Y
authors: Wu
mesh_terms: D000085:Acetates / Q000737:chemistry; D000001:Calcimycin / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D004164:Diphosphonates / Q000737:chemistry; D006861:Hydrogen Peroxide / Q000737:chemistry; D061065:Polyketides / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000085:Acetates; D004164:Diphosphonates; C118890:Oxonia Active; D061065:Polyketides; D000001:Calcimycin; C036715:cezomycin; D006861:Hydrogen Peroxide
keywords: Aldol reaction; allylation; migration; polyketides; rearrangement