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Complete Stereocontrol in Organocatalytic Additions of β‐Ketosulfoxides to Conjugated Aldehydes
Author(s) -
García Ruano José Luis,
Alvarado Cuauhtémoc,
DíazTendero Sergio,
Alemán José
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201003267
Subject(s) - nucleophile , electrophile , diastereomer , chemistry , chirality (physics) , reagent , conjugated system , asymmetric carbon , catalysis , sulfur , optically active , chiral auxiliary , organocatalysis , combinatorial chemistry , enantioselective synthesis , organic chemistry , computational chemistry , symmetry breaking , chiral symmetry breaking , physics , polymer , quantum mechanics , nambu–jona lasinio model
The use of β‐ketosulfoxides as nucleophiles in reactions with α,β‐unsaturated aldehydes catalyzed by proline derivatives allows complete control of configuration at the two chiral centers that are created during 1,4‐addition reactions. The sulfinyl group can be used to create additional chiral centers in the resulting compounds and then removed while preserving the chirality of the carbon joined to the sulfur. The catalyst and the sulfinyl group are mainly responsible for the configurational control of the carbon atoms acting as electrophile and nucleophile, respectively, which allows the preparation of the four possible diastereoisomers in optically pure form. Theoretical calculations of the possible chiral nucleophilic species bearing diastereotopic faces allow us to postulate, for the first time, that enolates, instead of enols, are the active reagents in these reactions.