Catalytic Cyclization of o‐Alkynyl Phenethylamines via Osmacyclopropene Intermediates: Direct Access to Dopaminergic 3‐Benzazepines

NOTICE: This is the peer reviewed version of the following article: Álvarez-Pérez, A., González-Rodríguez, C., García-Yebra, C., Varela, J. A., Oñate, E., Esteruelas, M. A., Saá, C. (2015). Catalytic Cyclization of o‐Alkynyl Phenethylamines via Osmacyclopropene Intermediates: Direct Access to Dopaminergic 3‐Benzazepines. Angew. Chem. Int. Ed., 54, 45, 13357-13361. [doi: 10.1002/anie.201505782]. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for self-archivingA 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.This work was supported by MICINN (projects CTQ2011-28258, CTQ2014-52799-P, and CTQ2014-51912REDC), Xunta de Galicia and European Regional Development Fund (projects GRC2014/032 and EM 2012/051), the DGA (E-35) and the European Social Fund (SFE). A. A.-P. and C. G.-R. thank Spanish MICINN for a predoctoral FPI fellowship and Juan de la Cierva Contract (JCI-2011-09946), respectivelyS

Catalytic cyclization of o-alkynyl phenethylamines via osmacyclopropene intermediates: direct access to dopaminergic 3-benzazepines

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.This research was supported by the MICINN (projects CTQ2011-28258, CTQ2014-52799-P, and CTQ2014-51912REDC), Xunta de Galicia and the European Regional Development Fund (projects GRC2014/032 and EM 2012/051), the DGA (E-35), and the European Social Fund (SFE). A.A.-P.and C.G.-R. thank the Spanish MICINN for a pre-doctoral FPI fellowship and Juan de la Cierva Contract (JCI-2011-09946), respectively.Peer Reviewe