Solvent-controlled stereoselective formation of a cyclic ether in the Lewis acid-mediated allylation of an α-chloroacetoxy acyclic ether. Very high stereoselectivity in CH3CN vs low stereoselectivity in CH 2Cl2

Journal of Organic Chemistry

Volumn 72, Issue 22, 2007, Pages 8371-8375

  Gridnev, Ilya D ^a   Kikuchi, Shigetoshi ^a   Touchy, Abeda S ^a   Kadota, Isao ^b   Yamamoto, Yoshinori ^a  

^a TOHOKU UNIVERSITY   (Japan)

^b OKAYAMA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALLYLATION; BREVETOXIN B; ETHER RINGS; MODEL COMPOUNDS; TRANSITION STATES;

ACTIVATION ENERGY; COORDINATION REACTIONS; CYCLIZATION; ISOMERS; MIXTURES; SOLVENTS; STEREOSELECTIVITY;

ETHERS;

ACETONITRILE; ALPHA CHLOROACETOXY ACYCLIC ETHER; BREVETOXIN; BREVETOXIN B; DICHLOROMETHANE; ETHER DERIVATIVE; LEWIS ACID; MAGNESIUM DERIVATIVE; SOLVENT; UNCLASSIFIED DRUG;

ALLYLATION; ARTICLE; CHEMICAL STRUCTURE; CYCLIZATION; DENSITY FUNCTIONAL THEORY; DIASTEREOISOMER; ENERGY TRANSFER; STEREOCHEMISTRY;

ACETONITRILES; ACIDS; ALKYLATION; CYCLIZATION; ETHERS, CYCLIC; METHYLENE CHLORIDE; MODELS, CHEMICAL; MOLECULAR CONFORMATION; SOLVENTS; STEREOISOMERISM;

EID: 35548971640     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo7013752     Document Type: Article

References (15)

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5. Computations were performed on the B3LYP/SDD level of theory with the Gaussian 03 software package (see the Supporting Information for the reference and computational details).
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15. We were able to reproduce this result computationally. Thus, the optimized geometry of alkylnitrilium salt 6e (eis) is close to that of 6e (trans) (the bond-forming distances are 3.13 and 3.26 Å, respectively), and is only 0.4 kcal/mol higher in energy.