Regular Article
Ligand distortion modes leading to increased chirality content of Katsuki-Jacobsen catalysts
Kenny B. Lipkowitz,
Sabine Schefzick,
Corresponding Author
Kenny B. Lipkowitz
Department of Chemistry, Indiana University-Purdue University at Indianapolis (IUPUI), Indianapolis, Indiana
Department of Chemistry, IUPUI, 402 N. Blackford Street, Indianapolis, IN 46202Search for more papers by this authorSabine Schefzick
Department of Chemistry, Indiana University-Purdue University at Indianapolis (IUPUI), Indianapolis, Indiana
Search for more papers by this authorKenny B. Lipkowitz,
Sabine Schefzick,
Corresponding Author
Kenny B. Lipkowitz
Department of Chemistry, Indiana University-Purdue University at Indianapolis (IUPUI), Indianapolis, Indiana
Department of Chemistry, IUPUI, 402 N. Blackford Street, Indianapolis, IN 46202Search for more papers by this authorSabine Schefzick
Department of Chemistry, Indiana University-Purdue University at Indianapolis (IUPUI), Indianapolis, Indiana
Search for more papers by this authorAbstract
The “chirality content” of Katsuki-Jacobsen epoxidation catalysts are computed with the Avnir continuous chirality measure (CCM). An assessment of Mn(salen) molecules from the Cambridge Structural Database shows there exist some variation in CCM and the chirality content for several triplet state complexes of these catalysts purported in the literature to be the active species show even larger CCM values. Several deformation modes were analyzed to examine how chirality content changes as catalyst distortion is induced. The deformations studied include in-plane deformations, cup-shaped puckering, ligand twisting motions, and step-like deformations. Some distortions lead to increases of chirality while others lead to a decrease in chirality content. The most influential distortion modes that can be used for ligand design are twisting and step induction. Chirality 14:677–682, 2002. © 2002 Wiley-Liss, Inc.
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