Cross-Coupling Reaction of tert-Alkyl halides with Grignard Reagents in Dichloromethane as a Non-Lewis Basic Medium

Article abstract of DOI:10.1021/jo00239a005

In dichloromethane as a non-Lewis basic solvent, 1-haloadamantane 1 underwent a cross-coupling reaction with Grignard reagents to give bridgehead-substituted products 3-16 in moderate yields.In this case the same kind of halogen in both 1 and a Grignard reagent was favored; if not, functional exchange (i.e., 1a to 1c) occurred first.The reaction using 5-hexenylmagnesium bromide as a radical probe afforded uncyclized/cyclized coupling products in a 6/4 ratio.These fact suggested the significant participation of the single-electron-transfer process in these reactions.The present method could be extended to tert-butylation with some Grignard reagents.Interestingly, 1,3-dichloro-3-methylbutane coupled with butylmagnesium chloride selectively at the tertiary position. for the above displacement reaction of 1, an organozinc was also found to be effective.