Catalytic asymmetric intermolecular stetter reaction of enals with nitroalkenes: Enhancement of catalytic efficiency through bifunctional additives

Journal of the American Chemical Society

Volumn 133, Issue 27, 2011, Pages 10402-10405

  Dirocco, Daniel A ^a   Rovis, Tomislav ^a  

^a Department of Environmental and Radiological Health Sciences   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BIFUNCTIONAL; CATALYST LOADINGS; CATALYTIC EFFICIENCIES; CHIRAL N-HETEROCYCLIC CARBENES; GOOD YIELD; HIGH SELECTIVITY; NITROALKENES; PROTIC CONDITIONS; STETTER REACTION;

CARBON INORGANIC COMPOUNDS; PHENOLS; REACTION RATES;

ORGANIC COMPOUNDS;

ALDEHYDE DERIVATIVE; ALKENE DERIVATIVE; CARBENE; CATECHOL; HETEROCYCLIC COMPOUND;

ARTICLE; ASYMMETRIC INTERMOLECULAR STETTER REACTION; CATALYSIS; CATALYST; CHEMICAL REACTION; REACTION ANALYSIS; REACTION TIME;

ALKENES; CATALYSIS; CATECHOLS; HETEROCYCLIC COMPOUNDS; METHANE; NITRO COMPOUNDS; OXIDATION-REDUCTION;

EID: 79960063988     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja203810b     Document Type: Article

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26. The role of a solvent isotope effect in this reaction cannot be discounted. However, an experimental value of an isotope effect of 3.6 for the hydration of acetaldehyde has been explained by the intervention of three molecules of water in the addition step, ultimately involving the cleavage of O-H (O-D) bonds. A theoretical investigation of the hydration of formaldehyde supports this assertion; to wit, the isotope effect is due not to solvent but to a specific isotope effect (see: Wolfe, S.; Kim, C.-K.; Yang, K.; Weinberg, N.; Shi, Z. J. Am. Chem. Soc. 1995, 117, 4240-4260 and references therein) It is also noteworthy that the entropically disfavored intervention of three water molecules in this reaction is preferred because of the preference for the eight-membered ring for the proton tranfer events, with the larger O-H-O bond angles it facilitates. We further note that the catecholate also forms an eight-membered ring in our proposed model for shuttling of the proton from C to O.