A direct aminocatalytic synthesis has been developed for the chemo-, regio-, diastereo-, and enantioselective construction of densely substituted polycyclic carbaldehydes containing fused cyclohexadiene rings. The chemistry utilizes, for the first time, remotely enolizable pi-extended allylidenemalononitriles as electron-rich 1,3-diene precursors in a direct eliminative [4+2] cycloaddition with both aromatic and aliphatic alpha,beta-unsaturated aldehydes. The generality of the process is demonstrated by approaching 6,6-, 5,6-, 7,6-, 6,6,6-, and 6,5,6-fused ring systems, as well as biorelevant steroid-like 6,6,6,6,5- and 6,6,6,5,6-rings. A stepwise reaction mechanism for the key [4+2] addition is proposed as a domino bisvinylogous Michael/Michael/retro-Michael reaction cascade. The utility of the malononitrile moiety as traceless activating group of the dicyano nucleophilic substrates is demonstrated.

Organocatalytic, Asymmetric Eliminative [4+2] Cycloaddition of Allylidene Malononitriles with Enals: Rapid Entry to Cyclohexadiene-Embedding Linear and Angular Polycycles / Brindani, Nicoletta; Rassu, Gloria; Dell'Amico, Luca; Zambrano, Vincenzo; Pinna, Luigi; Curti, Claudio; Sartori, Andrea; Battistini, Lucia; Casiraghi, Giovanni; Pelosi, Giorgio; Greco, Daniela; Zanardi, Franca. - In: ANGEWANDTE CHEMIE. - ISSN 1521-3773. - 54:(2015), pp. 7386-7390. [10.1002/anie.201501894]

Organocatalytic, Asymmetric Eliminative [4+2] Cycloaddition of Allylidene Malononitriles with Enals: Rapid Entry to Cyclohexadiene-Embedding Linear and Angular Polycycles

BRINDANI, Nicoletta;DELL'AMICO, LUCA;CURTI, Claudio;SARTORI, Andrea;BATTISTINI, Lucia;CASIRAGHI, Giovanni;PELOSI, Giorgio;GRECO, Daniela;ZANARDI, Franca
2015

Abstract

A direct aminocatalytic synthesis has been developed for the chemo-, regio-, diastereo-, and enantioselective construction of densely substituted polycyclic carbaldehydes containing fused cyclohexadiene rings. The chemistry utilizes, for the first time, remotely enolizable pi-extended allylidenemalononitriles as electron-rich 1,3-diene precursors in a direct eliminative [4+2] cycloaddition with both aromatic and aliphatic alpha,beta-unsaturated aldehydes. The generality of the process is demonstrated by approaching 6,6-, 5,6-, 7,6-, 6,6,6-, and 6,5,6-fused ring systems, as well as biorelevant steroid-like 6,6,6,6,5- and 6,6,6,5,6-rings. A stepwise reaction mechanism for the key [4+2] addition is proposed as a domino bisvinylogous Michael/Michael/retro-Michael reaction cascade. The utility of the malononitrile moiety as traceless activating group of the dicyano nucleophilic substrates is demonstrated.
Organocatalytic, Asymmetric Eliminative [4+2] Cycloaddition of Allylidene Malononitriles with Enals: Rapid Entry to Cyclohexadiene-Embedding Linear and Angular Polycycles / Brindani, Nicoletta; Rassu, Gloria; Dell'Amico, Luca; Zambrano, Vincenzo; Pinna, Luigi; Curti, Claudio; Sartori, Andrea; Battistini, Lucia; Casiraghi, Giovanni; Pelosi, Giorgio; Greco, Daniela; Zanardi, Franca. - In: ANGEWANDTE CHEMIE. - ISSN 1521-3773. - 54:(2015), pp. 7386-7390. [10.1002/anie.201501894]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11381/2790191
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