Unimolecular net heterolysis of symmetric and homopolar σ-bonds.

The unimolecular heterolysis of covalent σ-bonds is integral to many chemical transformations, including S N 1-, E1- and 1,2-migration reactions. To a first approximation, the unequal redistribution of electron density during bond heterolysis is governed by the difference in polarity of the two departing bonding partners 1-3 . This means that if a σ-bond consists of two identical groups (that is, symmetric σ-bonds), its unimolecular fission from the S 0 , S 1 , or T 1 states only occurs homolytically after thermal or photochemical activation 1-7 . To force symmetric σ-bonds into heterolytic manifolds, co-activation by bimolecular noncovalent interactions is necessary 4 . These tactics are only applicable to σ-bond constituents susceptible to such polarizing effects, and often suffer from inefficient chemoselectivity in polyfunctional molecules. Here we report the net heterolysis of symmetric and homopolar σ-bonds (that is, those with similar electronegativity and equal leaving group ability 3 ) by means of stimulated doublet-doublet electron transfer (SDET). As exemplified by Se-Se and C-Se σ-bonds, symmetric and homopolar bonds initially undergo thermal homolysis, followed by photochemically SDET, eventually leading to net heterolysis. Two key factors make this process feasible and synthetically valuable: (1) photoexcitation probably occurs in only one of the incipient radical pair members, thus leading to coincidental symmetry breaking 8 and consequently net heterolysis even of symmetric σ-bonds. (2) If non-identical radicals are formed, each radical may be excited at different wavelengths, thus rendering the net heterolysis highly chemospecific and orthogonal to conventional heterolyses. This feature is demonstrated in a series of atypical S N 1 reactions, in which selenides show SDET-induced nucleofugalities 3 rivalling those of more electronegative halides or diazoniums.