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Titolo:
Computational explorations of vinylcyclopropane-cyclopentene rearrangements and competing diradical stereoisomerizations
Autore:
Nendel, M; Sperling, D; Wiest, O; Houk, KN;
Indirizzi:
Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA Univ Calif Los Angeles Los Angeles CA USA 90095 Los Angeles, CA 90095 USA Univ Notre Dame, Dept Chem & Biochem, Notre Dame, IN 46556 USA Univ Notre Dame Notre Dame IN USA 46556 Biochem, Notre Dame, IN 46556 USA
Titolo Testata:
JOURNAL OF ORGANIC CHEMISTRY
fascicolo: 11, volume: 65, anno: 2000,
pagine: 3259 - 3268
SICI:
0022-3263(20000602)65:11<3259:CEOVR>2.0.ZU;2-D
Fonte:
ISI
Lingua:
ENG
Soggetto:
THERMAL UNIMOLECULAR VINYLCYCLOPROPANE; STEREOCHEMISTRY; ISOMERIZATIONS; CYCLOPROPANE; KINETICS; CONCERT; STATES;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Life Sciences
Physical, Chemical & Earth Sciences
Citazioni:
62
Recensione:
Indirizzi per estratti:
Indirizzo: Houk, KN Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA Univ Calif Los Angeles Los Angeles CA USA 90095 es, CA 90095 USA
Citazione:
M. Nendel et al., "Computational explorations of vinylcyclopropane-cyclopentene rearrangements and competing diradical stereoisomerizations", J ORG CHEM, 65(11), 2000, pp. 3259-3268

Abstract

The rearrangements and stereoisomerizations of four systems, vinylcyclopropane, 4-tert-butylvinylcyclopropane, 5-methylvinylcyclopropane, and 2,5-dimethylvinylcyclopropane, as well as a variety of deuterated derivatives and 1- and 2-methyl-, methoxy-, difluoro-, and amino-substituted species, were studied by density functional theory calculations using the B3LYP functional and the 6-31G* basis set. Energies were evaluated with CASSCF(4,4)/6-31G*single point calculations. The major product is obtained by the si pathway. Structures on this path are essentially pure diradical in character. Higher energy diradical species and intermediates are responsible for the scrambling of the stereochemistry. The stereoselectivity of the reaction is increased by substituents which increase the relative energy of the species involved in competing stereoselectivities. The computed secondary kinetic isotope effects reproduce the experimental values reported in the literature.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 04/12/20 alle ore 14:58:46