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Stereochemistry and Mechanistic Study of Intramolecular Pd II ‐Catalyzed Oxypalladation and 1,3‐Chirality‐Transfer Reactions
Author(s) -
Uenishi Jun'ichi,
Vikhe Yogesh Shankar,
Kawai Nobuyuki
Publication year - 2008
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.200700390
Subject(s) - allylic rearrangement , intramolecular force , chirality (physics) , chemistry , stereochemistry , catalysis , stereospecificity , alcohol , ring (chemistry) , asymmetric carbon , medicinal chemistry , reaction mechanism , chiral symmetry , organic chemistry , physics , optically active , quantum mechanics , nambu–jona lasinio model , quark
Abstract Pd II ‐catalyzed cyclizations of chiral ε‐, ζ‐, and η‐hydroxy‐α,β‐unsaturated alcohols are described. The reactions took place stereospecifically to give chiral 2,5‐disubstituted tetrahydrofurans, 2,6‐disubstituted tetrahydropyrans, and 2,7‐disubstituted oxepanes, respectively. The chirality of the carbon center of the chiral allylic alcohol is transferred stereospecifically to the carbon center of the newly generated oxacyclic ring. A plausible reaction mechanism involves 1) chiral‐allylic‐alcohol‐induced syn facioselective formation of a Pd π‐complex, 2) syn oxypalladation, and 3) syn elimination of PdCl(OH), which provide a rational account for the stereochemical results.