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Mechanism and selectivity of cinchona alkaloid catalyzed [1,3]-shifts of allylic trichloroacetimidates.

ABSTRACT: Density functional theory calculations were used to investigate the [3,3]- and [1,3]-shifts of O-allylic trichloroacetimidates in the presence of cinchona alkaloids. Thermal [1,3]- and [3,3]-rearrangements proceed through concerted pseudopericyclic transition states to give the corresponding rearranged products. [1,3]-Rearrangement is catalyzed via a double S(N)2' mechanism in which syn addition of the nucleophile is exclusively preferred in both steps. The catalyzed mechanism is favored by a 6.3 kcal/mol free energy difference compared to the alternative [3,3]-rearrangement pathway. The fast-reacting enantiomer is predicted to be determined by the availability of the H-bonding interaction between the catalyst and the substrate.

SUBMITTER: Celebi-Olcum N

PROVIDER: S-EPMC2748823 | biostudies-literature | 2009 Sep

REPOSITORIES: biostudies-literature

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Mechanism and selectivity of cinchona alkaloid catalyzed [1,3]-shifts of allylic trichloroacetimidates.

Celebi-Olçüm Nihan N Aviyente Viktorya V Houk K N KN

The Journal of organic chemistry 20090901 18

Density functional theory calculations were used to investigate the [3,3]- and [1,3]-shifts of O-allylic trichloroacetimidates in the presence of cinchona alkaloids. Thermal [1,3]- and [3,3]-rearrangements proceed through concerted pseudopericyclic transition states to give the corresponding rearranged products. [1,3]-Rearrangement is catalyzed via a double S(N)2' mechanism in which syn addition of the nucleophile is exclusively preferred in both steps. The catalyzed mechanism is favored by a 6. ...[more]

PMID: 19689147

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