Activation and functionalization of C−H bonds has become one of the most useful methods in organic synthesis as it allows the formation of structurally complex molecules in an efficient and atom‑economical fashion.[1] Of all the transition metals able to promote this transformation, rhodium(III) has been extensively studied and numerous aromatic and vinylic C(sp2)-H bonds activations have been reported.[2] However, despite its very high interest, the more challenging Rh(III)‑catalyzed activation of C(sp3)-H bonds is still very rare.[3] We have developed a new Rh(III)-promoted transformation of unsaturated N-tosylamides implying the insertion of diarylalkynes in an allylic C(sp3)−H bond. This unusual reaction generates 1‑azabicyclo[n.3.0]alkenes in good yields and allows a high diastereoselective control of three contiguous stereogenic centers. [1] Transitions Metals for Organic Chemistry, 2nd ed. (Eds.: Beller, M; Bolm, C.), Wiley-VCH, Weinheim, 2004. [2] Song. G.; Wang, F.; Li, X. Chem. Soc. Rev. 2012, 41, 3651-3678. [3] (a) Rakshit, S.; Patureau, F. W.; Glorius, F. J. Am. Chem. Soc. 2010, 132, 9585-9587. (b) Cochet, T.; Bellosta, V.; Roche, D.; Ortholand, J.-Y.; Greiner, A.; Cossy, J. Chem. Commun. 2012, 48, 10745-10747. (c) Liu, B.; Zhou, T.; Li, B.; Xu, S.; Song, H.; Wang, B. Angew. Chem. Int. Ed. 2014, 53, 4191-4195.

Rh(III)-catalyzed C(sp3)H allylic functionalization of N-tosylamides :An unexpected formation of azabicyclic compounds

249th National Meeting (2015)

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