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The Direct, Enantioselective, One‐Pot, Three‐Component, Cross‐Mannich Reaction of Aldehydes: The Reason for the Higher Reactivity of Aldimine versus Aldehyde in Proline‐Mediated Mannich and Aldol Reactions
Author(s) -
Hayashi Yujiro,
Urushima Tatsuya,
Shoji Mitsuru,
Uchimaru Tadafumi,
Shiina Isamu
Publication year - 2005
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.200505190
Subject(s) - aldimine , chemistry , benzaldehyde , aldehyde , aldol reaction , nucleophile , mannich reaction , reactivity (psychology) , electrophile , enantioselective synthesis , organic chemistry , medicinal chemistry , catalysis , medicine , alternative medicine , pathology
In the proline‐mediated Mannich and aldol reactions of propanal as a nucleophile, the aldimine prepared from benzaldehyde and p ‐anisidine is about 7 times more reactive than the corresponding aldehyde, benzaldehyde, as an electrophile. This higher reactivity of aldimine over aldehyde is attributed to the carboxylic acid of proline protonating the basic nitrogen atom of the aldimine more effectively than the oxygen atom of the aldehyde, an explanation which has been both experimentally and theoretically verified.