A Novel Allyl Transfer Coupled with a Grob Fragmentation |
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| Authors: | Dr. Shao‐Gang Li Dr. Hui‐Jun Chen Yang‐Yang Yang Wen‐Ju Wu Prof. Dr. Yikang Wu |
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| Affiliation: | 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, Shanghai, China |
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| 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. |
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| Keywords: | Aldol reaction allylation migration polyketides rearrangement |
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