Conférence NARC 26/03

Prof. Pier Giorgio Cozzi present "Playing with carbenium ion: From Quantum Cellular Automata to Stereoselective Synthesis of Isoquinoline Alkaloids"

Recently, the direct substitution of allylic, benzylic and tertiary alcohols has be achieved via an SN1 reaction with catalytic amount of Brønsted or Lewis acids.1 During recent years our group was exploring the reactivity of carbenium ion for material chemistry and organocatalysis The stability of ferrocenyl carbenium ion was quite effective in realizing new SN1 type reactions and apply the chemistry to the preparation of structures for quantum cellular automata (QCA).2 In addition, we have used stabilized carbenium ion, directly available or obtained by the corresponding alcohols, in new organocatalytic stereoselective SN1-type reactions.3 The key concepts of activation modes in organocatalysis will be illustrated through the Mayr scale of reactivity, as bridging element of this lecture. Stabilized carbenium ions can be used for material science and for organocatalysis. As valuable application of SN1-type reaction in organocatalysis, we will report the development of simple and highly enantioselective addition of aldehydes to isoquinolines.4 Application of this methodology in total synthesis of natural products and preparation of valuable starting material will be also presented.

(1). Emer, E.; Sinisi, R.; Guiteras Capdevila, M.; Petruzziello, D.; De Vincentiis, F.; Cozzi P. G., Eur. J. Org. Chem. 2011, 647-662.

(2) Arima, V.; Iurlo, M.; Zoli, L.; Kumar, S.; Piacenza, M.; Della Sala, F.; Matino, F.; Maruccio, G.; Rinald, R.; Paolucci, F.; Marcaccio, M.; Cozzi, P.G.; Bramanti, A.P. , Nanoscale, 2012, 4, 813-824.

(3). Gualandi, A.; Cozzi, P. G., Synlett 2013, 24, 281-296.

(4) Mengozzi, L; Gualandi, A.; Cozzi, P. G., Chem. Sci. 2014, 5, 3915-3921.

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