A radical rearrangement

A radical thia-Brook rearrangement.

Geminal mercapto trialkyl- and trialkoxy-silanes undergo an efficient radical chain rearrangement, whereby the silyl group migrates from carbon to sulfur; the starting materials are readily obtained by exploiting the peroxide initiated radical addition of dithiocarbonates (xanthates) to trialkyl- or trialkoxy-vinylsilanes.

Radical Smiles Rearrangement: An Update.

Over the decades the Smiles rearrangement and its variants have become essential synthetic tools in modern synthetic organic chemistry. In this mini-review we summarized some very recent results of the radical version of these rearrangements. The selected examples illustrate the synthetic power of this approach, especially if it is incorporated into a domino process, for the preparation of poly...

First domino radical cyclisation/Smiles rearrangement combination.

An unprecedented domino radical cyclisation-Smiles rearrangement process affording 3-(2'-aryl-N-methyl acetamido)indolin-2-ones is presented. Experimental rationalisation of this approach and description of an unexpected tricyclic core are also handled.

The radical cation of syn-tricyclooctadiene and its rearrangement products

The syn dimer of cyclobutadiene (tricyclo[4.2.0.0(2.5)]octa-3,7-diene, TOD) is subjected to ionization under different conditions and the resulting species are probed by optical and ESR spectroscopy. By means of quantum chemical modelling of the potential energy surfaces and the optical spectra, it is possible to assign the different products that arise spontaneously after ionization or after s...

Quantum Chemical Studies of Radical Cation Rearrangement, Radical Carbonylation, and Homolytic Substitution Reactions