Joint Experimental, in Silico, and NMR Studies toward the Rational Design of Iminium-Based Organocatalyst Derived from Renewable Sources

An efficient organocatalyst for iminium-ion based asymmetric Diels–Alder (DA) reactions has been rationally designed. The most influential structure–activity relationships were determined experimentally, while DFT calculations and NMR studies provided further mechanistic insight. This knowledge guid...

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Bibliographic Details
Published in:Journal of organic chemistry 2015-08, Vol.80 (15), p.7626-7634
Main Authors: Gerosa, Gabriela G, Spanevello, Rolando A, Suárez, Alejandra G, Sarotti, Ariel M
Format: Article
Language:English
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Summary:An efficient organocatalyst for iminium-ion based asymmetric Diels–Alder (DA) reactions has been rationally designed. The most influential structure–activity relationships were determined experimentally, while DFT calculations and NMR studies provided further mechanistic insight. This knowledge guided an in silico screening of 62 different catalysts using an ONIOM­(B3LYP/6-31G*:AM1) transition-state modeling, which showed good correlation between theory and experiment. The top-scored compound was easily synthesized from levoglucosenone, a biomass-derived chiral enone, and evaluated in the DA reaction between (E)-cinnamaldehyde and cyclopentadiene. In line with the computational finding, excellent results (up to 97% ee) were obtained. In addition, the catalyst could be easily recovered and reused with no loss in its catalytic activity.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.5b01214