Copper-catalyzed regioselective C2-H chlorination of indoles with para -toluenesulfonyl chloride.

A copper-catalyzed, pyrimidine directed regioselective C-H chlorination of indoles with para -toluenesulfonyl chloride (TsCl) has been developed. The reactions proceeded smoothly in the presence of 20 mol% of Cu(OAc) 2 as the catalyst and TsCl as the chlorine source, delivering C2-chlorinated indoles with structural diversity in moderate to excellent yields. Mechanistic studies suggested that single electron transfer (SET) from Cu(II) to TsCl accompanied by the release of the p -toluenesulfonyl radical and the related Cu(III)Cl species might be involved in the reactions.