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Organocatalytic, asymmetric eliminative [4+2] cycloaddition of allylidene malononitriles with enals: rapid entry to cyclohexadiene-embedding linear and angular polycycles

Brindani, Nicoletta and Rassu, Gloria Maria Rita and Dell'Amico, Luca and Zambrano, Vincenzo and Pinna, Luigi and Curti, Claudio and Sartori, Andrea and Battistini, Lucia and Casiraghi, Giovanni and Pelosi, Giorgio and Greco, Daniela and Zanardi, Franca (2015) Organocatalytic, asymmetric eliminative [4+2] cycloaddition of allylidene malononitriles with enals: rapid entry to cyclohexadiene-embedding linear and angular polycycles. Angewandte Chemie. International Edition, Vol. 54 (25), p. 7386-7390. eISSN 1521-3773. Article.

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DOI: 10.1002/anie.201501894

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 π-extended allylidenemalononitriles as electron-rich 1,3-diene precursors in a direct eliminative [4+2] cycloaddition with both aromatic and aliphatic α,β-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 bis-vinylogous Michael/Michael/retro-Michael reaction cascade. The utility of the malononitrile moiety as traceless activating group of the dicyano nucleophilic substrates is demonstrated.

Item Type:Article
ID Code:10957
Status:Published
Refereed:Yes
Uncontrolled Keywords:Asymmetric catalysis, carbocycles, cycloaddition, organocatalysis, synthetic methods
Subjects:Area 03 - Scienze chimiche > CHIM/06 Chimica organica
Divisions:001 Università di Sassari > 01-a Nuovi Dipartimenti dal 2012 > Chimica e Farmacia
002 Altri enti e centri di ricerca del Nord Sardegna > CNR-Consiglio Nazionale delle Ricerche > Istituto di chimica biomolecolare, Sassari
Publisher:Wiley
eISSN:1521-3773
Deposited On:11 Jun 2015 16:59

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