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Stereoselective Catalysis: History
Please note this is an old version of this entry, which may differ significantly from the current revision.
Subjects: Chemistry, Organic
Contributor: Helena Kang

Stereoselective catalysis comprises catalytic transformations in which one stereoisomer is formed preferentially over other constitutionally identical stereoisomers. Selectivity may be enantioselective, favoring one enantiomer, or diastereoselective, favoring one diastereomer; it is quantified by enantiomeric ratio, enantiomeric excess, diastereomeric ratio, or related stereochemical measures. A chiral catalyst creates diastereomeric transition states from an achiral or prochiral substrate and lowers their activation barriers unequally, whereas an achiral catalyst may still produce substrate-controlled diastereoselection [1]. Catalytic asymmetric hydrogenation exemplifies enantiotopic-face discrimination by a chiral metal complex [2]. The defining feature is kinetic discrimination within a catalytic cycle, not merely isolation of a single stereoisomer after a nonselective reaction. Stereoselective catalysis is therefore broader than enantioselective catalysis, but narrower than stereospecific reaction: stereospecificity maps different substrate stereoisomers to different products, while stereoselectivity concerns unequal product formation from a common substrate.

  • stereoselective catalysis
  • asymmetric catalysis
  • enantioselectivity
  • diastereoselectivity

Asymmetric Synthesis and Catalysis • Organic Chemistry • Chemistry • Physical Sciences

References

  1. Tehshik P. Yoon; Eric N. Jacobsen; Privileged Chiral Catalysts. Science 2003, 299, 1691-1693, 10.1126/science.1083622.
  2. William S. Knowles; Asymmetric hydrogenation. Accounts Chem. Res. 1983, 16, 106-112, 10.1021/ar00087a006.
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