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A novel osmium-catalyzed cyclization of o-alkynyl phenethylamines to give 3-benzazepines is reported. The procedure allows the straightforward preparation of a broad range of dopaminergic 3-benzazepine derivatives. Mechanistic investigations revealed that the process takes place via osmacyclopropene intermediates, which were isolated and characterized by X-ray crystallography.

Catalyst (I), readily available from the imidazolium salt and Pd(O-Ac)2, is isolated as an air-stable greyish solid, which exists in solution at room temperature as a mixture of diastereomers.

The previously unnoticed Ru complex activates the title reaction which proceeds under mild conditions and is fully diastereoselective.

Complex [(η6-p-cymene)OsCl(IPr)]OTf (1; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolylidene; OTf = CF3SO3) reacts with NaOH to give [(η6-p-cymene)Os(OH)(IPr)]OTf (2), which under hydrogen atmosphere affords [(η6-p-cymene)OsH3(IPr)]OTf (3). The hydride ligands of 3 undergo exchange coupling, decreasing the H−H coupling constant from 206 to 74 Hz in the temperature range 213−178 K. Complex 3 is also obtained in a two-step procedure involving the reaction of 2 with NaBH4 to give (η6-p-cymene)OsH2(IPr) (4) and the protonation of the latter with HOTf. Attempts to obtain 4 directly from 1 or (η6-p-cymene)OsCl2(IPr) (5) are unsuccessful. In both reactions (η6-p-cymene)OsHCl(IPr) (6) is formed. Complex 2 also reacts with methanol and 2-propanol. At −30 °C, the reaction with the first of them leads to [(η6-p-cymene)Os(OMe)(IPr)]OTf (7), while with the second one, [(η6-p-cymene)OsH{κ1-OC(CH3)2}(IPr)]OTf (8) is obtained. Complex 2 is a catalyst precursor for the hydrogen transfer from 2-propanol to aldehydes, which ...