Mechanistic subtleties in the cyclopentannelation of allenolate allyl carbamates: the origin of the center-to-center chirality transfer.
The stereospecific rearrangement of allene carbamates i to alkylidenecyclopentenones iii is concerted, displays charge donation from the pi*(allenonate) to the sigma*(C-leaving group), and shows mechanistic features of both pericyclic and ionic processes, modulated in part by the degree of ionic interaction (O-...Li+) in the putative intermediate allenolate ii.
Faza
Olalla Nieto
ON
Dpto. de Química Orgánica, Universidade de Vigo, Lagoas-Marcosende, 36310 Vigo, Spain.
López
Carlos Silva
CS
Alvarez
Rosana
R
de Lera
Angel R
AR