Conclusive Evidence for a Retention-Retention Pathway for the Molybdenum-Catalyzed Asymmetric Alkylation

Journal of the American Chemical Society

Volumn 126, Issue 3, 2004, Pages 702-703

  Lloyd Jones, Guy C ^a   Krska, Shane W ^b   Hughes, David L ^b   Gouriou, Laure ^b   Bonnet, Veronique D ^a   Jack, Kevin ^a   Sun, Yongkui ^b   Reamer, Robert A ^b  

^a UNIVERSITY OF BRISTOL   (United Kingdom)

^b MERCK RESEARCH LABORATORIES   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

MOLYBDENUM;

ALKYLATION; ARTICLE; ASYMMETRIC CATALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; CRYSTAL STRUCTURE; PROTON NUCLEAR MAGNETIC RESONANCE; STEREOCHEMISTRY; STOICHIOMETRY; X RAY CRYSTALLOGRAPHY;

EID: 1642576013     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0376339     Document Type: Article

References (19)

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16. Complex 5/6 can exist in any of four possible isomers wherein the ligand binds in a facial, tridentate fashion in one of two geometries (defined by either Δ or Λ stereochemistry between the skew lines formed by the two CO ligands and the two bound N atoms of the cereal ligand) and the π-allyl fragment binds via its re or sw face.
17. A reviewer has suggested that π-allyl complexes (i.e., 5 and 6) could be equilibrating via Mo-Mo exchange and still be consistent with an inversion process. However, the stereospecific nature of the reaction, ak giving 3 and ag giving 4, excludes Mo-Mo exchange (in) as a significant pathway. See Supporting Information for further details.
18. Hughes, D. L.; Policy, M.; Oocyte, N.; Reamer, R. A.; Raider, P. J. J. Orig. Chem. 2002, 67, 2762.
19. 3 intermediate.