Ec. Ashby et Ak. Deshpande, ELECTRON-TRANSFER IN THE REACTIONS OF GEMINAL DIHALIDES WITH PH(2)P(-) - EVIDENCE FOR THE FORMATION OF A CARBENE INTERMEDIATE FROM A RADICAL PRECURSOR, Journal of organic chemistry, 60(22), 1995, pp. 7117-7124
The reactions of two sterically hindered geminal dihalides, 6,6-dichlo
ro-5,5-dimethyl-1-hexene (5a) and 6,6-diiodo-5,5-dimethyl-1-hexene (5b
), with Ph(2)P(-) have been found to involve a single electron transfe
r (SET) pathway. Since the corresponding monochloride reacts with Ph(2
)P(-) by a S(N)2 pathway, it is clear that adding a second chlorine at
om on a carbon atom produces a more favorable reduction potential resu
lting in a change in mechanism from S(N)2 to SET. Evidence is also pre
sented that shows that the geminal dihalides produce carbene-derived p
roducts and that the carbene was derived from a haloalkyl radical prec
ursor.