Evidence for concerted processes in the course of the homoallenylic transposition

Chahinaz Aouf (1) , Nicolas Galy (2) , Maurice Santelli (3)

1 SPO - Sciences Pour l'Oenologie
2 TIMA - Techniques de l'Informatique et de la Microélectronique pour l'Architecture des systèmes intégrés
3 ICR - Institut de Chimie Radicalaire

The hydrolysis of beta-allenic tosylates produces mainly 2-methylenecyclobutanols resulting from a homoallenylic participation along with isomeric 2-methylenecyclobutanol minor products coming from a 1234-1243 rearrangement. Structures of various cyclopropylvinyl carbocations involved in the course of the hydrolysis have been determined by computational studies. For acyclic tosylates, the hydrolysis of one beta-deuterated allenic tosylate confirmed the nucleophilic attack on the corresponding nonclassical carbonium ion before its evolution to a more stable cyclopropylvinyl carbocation. In the case of one cyclic beta-allenic tosylate, the structure of the products has been checked by the use of deuterated isotopomer. (C) 2013 Published by Elsevier Ltd.

Domaines: Chimie

Chahinaz Aouf, Nicolas Galy, Maurice Santelli. Evidence for concerted processes in the course of the homoallenylic transposition. Tetrahedron, 2013, 69 (15), pp.3225--3233. ⟨10.1016/j.tet.2013.02.048⟩. ⟨hal-01460440⟩