Theoretical study of the asymmetric conjugate alkenylation of enones catalyzed by binaphthols

Journal of Organic Chemistry

Volumn 73, Issue 13, 2008, Pages 5078-5089

  Paton, Robert S ^a   Goodman, Jonathan M ^a   Pellegrinet, Silvina C ^b  

^a UNIVERSITY OF CAMBRIDGE   (United Kingdom)

^b Universidad Nacional de Rosario   (Argentina)

Author keywords

[No Author keywords available]

Indexed keywords

ATOMIC PHYSICS; ATOMS; CALCULATIONS; CARBONYLATION; CHEMICAL REACTIONS; IODINE; LIGANDS; NONMETALS; OXYGEN; PHOTOACOUSTIC EFFECT; RATE CONSTANTS;

(E ,3E) PROCESS; (R ,S)-CONJUGATE; ALKENYLBORONATES; AMERICAN CHEMICAL SOCIETY (ACS); ASYMMETRIC CONJUGATE ADDITION; BINAPHTHOL; BINAPHTHOLS; BORON ATOMS; CARBONYL OXYGEN; CATALYTIC CYCLING; CHEMICAL EQUATIONS; CONJUGATE ADDITIONS; DFT STUDY; EXPERIMENTAL RESULTS; FACTORS CONTROLLING; HETERO DIELS ALDER REACTION (HDA); IODINE ATOMS; LEWIS ACIDIC; METHOXY; REACTION CHANNELS; REACTIVITY (CHEMICAL); SUBSTITUENT EFFECTS; TRANSITION STRUCTURE (TS);

ADDITION REACTIONS;

ALKENE; BORON DERIVATIVE; CARBONYL DERIVATIVE; IODINE; LEWIS ACID; LIGAND; NAPHTHOL DERIVATIVE; OXYGEN;

ARTICLE; CATALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; COMPLEX FORMATION; ENANTIOMER; ENERGY; MOLECULAR INTERACTION; STEREOCHEMISTRY;

EID: 84961985396     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo8007463     Document Type: Article

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59. We performed similar calculations to study the effect of substitution on the alkenylboronate using binaphthol instead of 3,3′-diodobiphenol (4b) as a model for 3,3′-diiodobinaphthol (4a). The computed reactivity for 2b and 2c was nearly the same and slightly lower than that for 2d, while the enantiomeric ratios were ca. 99:1 for 2b and 2d and 98:2 for 2c, so model 4b predicts ratios that are closer to those obtained experimentally. These results might suggest that binaphthol could be a better ligand for the conjugate addition of 1,2-disubstituted alkenylboronates.