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Stereodivergent Enantioselective Synthesis by Exploiting Unusually Large Kinetic H/D Isotope Effects on Deprotonation
Author(s) -
Hoppe Dieter,
Paetow Mario,
Hintze Folker
Publication year - 1993
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.199303941
Subject(s) - deprotonation , kinetic isotope effect , enantioselective synthesis , deuterium , chemistry , stereospecificity , kinetic energy , base (topology) , tritium , stereochemistry , medicinal chemistry , computational chemistry , catalysis , organic chemistry , nuclear physics , physics , ion , mathematical analysis , mathematics , quantum mechanics
On deprotonation of chiral deuterated carbamates like the reaction of ( S )‐ 1 with sec ‐butyllithium to form ( R )‐ 2 , unusually high kinetic isotope effects k H / k D of 70 or greater are observed. These point to the participation of a quantum mechanical tunnel effect and can be exploited for enantioselective transformations based on the discrimination by the base of H and D in otherwise identical environments. The procedure is particularly suitable for highly selective syntheses of stereospecific deuterium‐ and tritium‐labeled alcohols.