Disparate roles of chiral ligands and molecularly imprinted cavities in asymmetric catalysis and chiral poisoning

Organometallics

Volumn 21, Issue 1, 2002, Pages 7-9

  Koh, Jeong Hwan ^a   Larsen, Andrew O ^a   White, Peter S ^a   Gagné, Michel R ^a  

^a University of North Carolina at Chapel Hill   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHIRAL CAVITY; IMPRINTED CAVITIES; LEWIS ACID CATALYSIS; METAL COMPLEXES;

CATALYSIS; CATALYST SELECTIVITY; CATALYSTS; MOLECULAR ORIENTATION; MOLECULAR STRUCTURE; REACTION KINETICS; STEREOCHEMISTRY;

COMPLEXATION;

EID: 0012217710     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om010944c     Document Type: Article

References (29)

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17. Poisoning has been used to modify MIPs for chromatography and binding; see: Kirsch, N.; Alexander, C.; Lübke, M.; Whitcombe, M. J.; Vulfson, E. N. Polymer 2000, 41, 5583-5590.
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19. 12 see also: Santora, B. P.; Gagné, M. R.; Moloy, K. G.; Radu, N. S. Macromolecules 2001, 34, 658-661.
20. C12 does not contain a BINOL ligand, it was similarly treated with HCl, though this was found not to affect reactivity or selectivity.
21. (S)-MeOBiphep gives the R ene product: (a) Hao, J.; Hatano, M.; Mikami, K. Org. Lett. 2000, 2, 4059-4062.
22. (b) Koh, J. H.; Larsen, A. O.; Gagné, M. R. Org. Lett. 2001, 3, 1233-1236.
23. Control experiments indicate that finely divided AgCl is not a catalyst; see the Supporting Information for details.
24. See the Supporting Information for details.
25. 3c,d
26. BINAM is a reversible poison, one that competes with, but does not exclude, substrate coordination.
27. 2+ binds to (S)-BINAM (>98:2) in preference to (R)-BINAM in competition experiments; see the Supporting Information for details. This unusual poisoning preference will be the subject of a future investigation.
28. In kinetic terms, ligand substitution is slower for a well-matched cavity and ligand, and so the BINAM poison accumulates in the well-defined sites. In this manner, the most well-matched sites for the poison are selectively retarded for catalysis, and surface sites dominate product output.
29. For a discussion, see: Tudor, M. D.; Becker, J. J.; White, P. S.; Gagné, M. R. Organometallics 2000, 19, 4376-4384.