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Theoretical insights into the regioselectivity of a Pictet‐Spengler reaction: Transition state structures leading to salsolinol and isosalsolinol
Author(s) -
Almodovar Iriux,
Rezende Marcos Caroli,
Cassels Bruce K.,
GarcíaArriagada Macarena
Publication year - 2017
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3666
Subject(s) - iminium , chemistry , regioselectivity , pictet–spengler reaction , acetaldehyde , zwitterion , reaction mechanism , computational chemistry , density functional theory , transition state , dopamine , ion , organic chemistry , catalysis , ethanol , molecule , neuroscience , biology
The mechanism of the cyclization step of the Pictet‐Spengler reaction between acetaldehyde and dopamine to give salsolinol and isosalsolinol was studied computationally, using density functional theory. The preferential formation in acidic media of salsolinol, the product of para ‐cyclization, and the requirement of a neutral pH for the formation of the ortho ‐cyclized isosalsolinol are explained in terms of 2 different mechanistic routes with an iminium ion or a phenolate‐iminium zwitterion as starting reactants.