Study toward the synthesis of (R)-(-)-aporphine

Study toward the synthesis of (R)-(-)-aporphine

Perecim, Givago P.; Raminelli, Cristiano

Abstract:

In view of the considerable importance of the benzyne chemistry in reactions of insertion into sigma bonds and cycloaddition reactions, which have been widely used in the synthesis of bioactive natural products and in preparations of functional materials, we decided to accomplish the total synthesis of (R)-(-)-aporphine (1), using as key step the [4+2] cycloaddition reaction, followed by spontaneous dehydrogenation, between methylene-isoquinoline (4) and benzyne (8), generated from 2-(trimethylsilyl)phenyl triflate (9), under mild reaction conditions.

In view of the considerable importance of the benzyne chemistry in reactions of insertion into sigma bonds and cycloaddition reactions, which have been widely used in the synthesis of bioactive natural products and in preparations of functional materials, we decided to accomplish the total synthesis of (R)-(-)-aporphine (1), using as key step the [4+2] cycloaddition reaction, followed by spontaneous dehydrogenation, between methylene-isoquinoline (4) and benzyne (8), generated from 2-(trimethylsilyl)phenyl triflate (9), under mild reaction conditions.

Palavras-chave:

DOI: 10.5151/chempro-15bmos-BMOS2013_2013913154342

Referências bibliográficas

• [1] 1(a) Tadross, P. M.; Stoltz, B. M. Chem. Rev. 2012, 112, 3550. (b) Gampe,
• [2] C. M.; Carreira, E. M. Angew. Chem., Int. Ed. 2012, 51, 3766.
• [3] 2(a) Lu, X.; Nikawa, H.; Tsuchiya, T.; Akasaka, T.; Toki, M.; Sawa, H.;
• [4] Mizorogi, N.; Nagase, S. Angew. Chem., Int. Ed. 2010, 49, 594. (b) Shen,
• [5] Y.-M.; Grampp, G.; Leesakul, N.; Hu, H.-W.; Xu, J.-H. Eur. J. Org. Chem.
• [6] 2007, 3718.
• [7] 3Atanes, N.; Castedo, L.; Guitián, E.; Saá, C.; Saá, J. M.; Suau, R. J. Org.
• [8] Chem. 1991, 56, 2984.
• [9] 4Atanes, N.; Castedo, L.; Cobas, A.; Guitián, E.; Saá, C.; Saá, J. M.
• [10] Tetrahedron 1989, 45, 7947.
• [11] 5Cava, M. P.; Stern, P.; Wakisaka, K. Tetrahedron 1973, 29, 2245.
• [12] 6Shi, X.-X.; Ni, F.; Shang, H.-X.; Yan, M.-L.; Su, J.-Q. Tetrahedron:
• [13] Asymmetry 2006, 17, 2210.

Como citar:

Perecim, Givago P.; Raminelli, Cristiano; "Study toward the synthesis of (R)-(-)-aporphine", p-233-233. In: In Blucher Chemistry Proceedings, São Paulo, v. 1, n. 2, Dezembro.2013. São Paulo: Blucher, 2013.
ISSN 23184043, DOI 10.5151/chempro-15bmos-BMOS2013_2013913154342