Carbon-carbon bond forming processes are important in organic synthesis, especially if these can be carried-out under catalytic and atom-economical conditions. Herein we present kinetic, computational and mechanistic studies on the titanocene-catalyzed intramolecular arylation of epoxide derived radicals.1   The unique characteristic of the titanocene-catalyzed process is the catalytic role of Ti(III) and collidine hydrochloride (Coll*HCl). Regeneration of active catalyst by an intramolecular electron transfer-proton transfer mechanism negates the use of stoichiometric reagents (other than substrate).2 The success of this reaction is critically dependant on a mechanism-based approach for tuning the stability and electronic properties of the catalyst. The role of Coll*HCl and other important mechanistic features of the reaction will be presented. References (1)   Gans�uer, A.; Fleckhaus, A.; Alejandre Lafont, M.; Okkel, A.; Kotsis, K.; Anoop, A.; Neese, F.  J. Am. Chem. Soc. 2009 , 131, 16989-16999.(2)   Gans�uer, A.; Behlendorf, M; Laufenberg, von D.; Kube C.; Sadasivam D. V.; Flowers R.A. II Angew. Chem. Int. Ed. 2012,  (In press).

Mechanistic investigation of catalytic, atom-efficient aromatic substitution through radical intermediates

244th National Meeting (2012)

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