1. Introduction The synthesis and neuropharmacological characterization of 10-deoxyapomorphine derivatives are a new and important direction in the development of potent and subtype selective dopaminergic and/or serotonergic ligands [1-6]. Currently all the synthetic methods towards deoxyapomorphines are based on the preparation of 3-O-(triluoromethyl)sulfonyl- morphine (2) or -oripavine (5), the acid-catalyzed rearrangement of these morphinans into aporphinoids and further manipulations on the sensitive aporphine backbone. Earlier procedures involved the synthesis and transformation of 3-(1-phenyltetrazoyl)morphine (3) [7,8], however the rearrangement of this compound gave rise to a mixture of aporphines and the hydrogenolytic removal of the (phenyltetrazolyl)oxy moiety from the aporphines was reported to be ‘erratic and capricious’ in both catalytic hydrogenolysis reactions and in catalytic hydrogen-transfer reactions [8,9]. Here we report a new, eficient and versatile route to 10-deoxyaporphines based on hitherto unknown 3-deoxyoripavine (7). The practical signiicance of this procedure is even higher due to the fact that the starting derivative of our procedure, oripavine (4), is now one of the major industrial poppy alkaloids [10-12]; especially since the discovery and growing cultivation of the poppy mutant known as top1 (for ‘thebaine oripavine poppy 1’) which led the island state of Tasmania to produce the major part of the world’s licit thebaine and oripavine directly from natural sources [10]. Central European Journal of Chemistry The irst synthesis of 3-deoxyoripavine and its utilization in the preparation of 10-deoxyaporphines and cyprodime # * E-mail: sipos.attila@pharm.unideb.hu # This paper is dedicated to the memory of Prof. Sándor Makleit who passed away on 27.09.2012 Received 14 January 2013; Accepted 19 March 2013 Abstract: © Versita Sp. z o.o. Keywords: Oripavine • Cyprodime • 10-deoxyaporphines • Reduction • Acid-catalyzed rearrangement 1 Department of Pharmaceutical Chemistry, Medical and Health Science Centre, University of Debrecen, H-4010 Debrecen, Hungary 2 Department of Physical Chemistry, University of Debrecen, H-4010 Debrecen, Hungary 3 Department of Organic Chemistry, University of Debrecen, H-4010 Debrecen, Hungary Attila Sipos 1* , Antal Udvardy 2 , Attila C. Bényei 1,2 , Sándor Berényi 3 Research Article The synthesis of 3-deoxyoripavine (7) was realized as a novel and promising intermediate towards the synthesis of the important class of dopaminergic and/or serotonergic 10-deoxyaporphines and the special pharmacological tool µ opioid antagonist cyprodime. Generally, the preparation of these valuable biologically active compounds was achieved in remarkable yields. 1278 Cent. Eur. J. Chem. • 11(8) • 2013 • 1278-1285 DOI: 10.2478/s11532-013-0256-x Author copy