ortho‐Palladation of a sterically crowded primary benzylamine, α‐phenylneopentylamine, was accomplished in a moderate yield of 50% in the reaction with the weakest of palladation agents (Li2PdCl4) under very mild conditions, due to a steric promotion of an aromatic C–H bond activation. The structure of dimer 1a thus formed and the palladacycle conformation were established on the basis of 1H‐NMR spectroscopy of its mononuclear derivatives with [D5]pyridine (3a) and triphenylphosphane (4a), and an X‐ray investi‐gation of the latter.
A new homochiral dimeric ortho-palladated complex bearing a bulky tert-butyl substituent at the carbon stereocenter was synthesized from optically active N,N-dimethyl-a-tertbutylbenzylamine. Regioselective activation of only the aromatic C--H bond was shown to occur during the cyclometallation process proceeding under verb' mild conditions due to steric effects. Spectral characteristics of mononuctear derivatives of the new dimeric complex indicate that the five-membered palladacycle exists predominantly in one of two possible chiral conformations with the axial position of the ten-butyl substituent.
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