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How Many Elementary Processes Are Involved in Base‐ and Acid‐Promoted Aldol Condensations?
Author(s) -
Yamabe Shinichi,
Hirahara Kohji,
Yamazaki Shoko
Publication year - 2007
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200700685
Subject(s) - chemistry , acetaldehyde , elementary reaction , reactivity (psychology) , aldol reaction , acetone , primary (astronomy) , medicinal chemistry , proton , bond cleavage , base (topology) , computational chemistry , molecule , organic chemistry , catalysis , kinetics , ethanol , medicine , physics , alternative medicine , pathology , quantum mechanics , astronomy , mathematical analysis , mathematics
The title reactions were investigated by density functional theory calculations. MeRC=O + OH – + (H 2 O) 8 (R = H and Me) and MeCH=O + H 3 O + + (H 2 O) 8 systems were adopted to trace the elementary processes. Eight water molecules were included to assure proton shifts through hydrogen bonds. The OH – ‐containing reactions were confirmed to have three elementary processes. Whereas the rate‐determining step of the reaction of acetaldehyde is C–H bond scission, that of acetone is C–C bond formation. The H 3 O + ‐containing reactions have two elementary processes. The reactivity difference between OH – ‐ and H 3 O + ‐promoted reactions was discussed in terms of their mobility and hydration strength. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)