{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Celebi-Olcum N"],"funding":["FIC NIH HHS","NIGMS NIH HHS"],"pagination":["6944-52"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC2748823"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["74(18)"],"pubmed_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."],"journal":["The Journal of organic chemistry"],"pubmed_title":["Mechanism and selectivity of cinchona alkaloid catalyzed [1,3]-shifts of allylic trichloroacetimidates."],"pmcid":["PMC2748823"],"funding_grant_id":["R03TW007177","R03 TW001318-03","R03 TW007177","GM36700","R01 GM036700-24","R37 GM036700","R01 GM036700"],"pubmed_authors":["Aviyente V","Houk KN","Celebi-Olcum N"],"additional_accession":[]},"is_claimable":false,"name":"Mechanism and selectivity of cinchona alkaloid catalyzed [1,3]-shifts of allylic trichloroacetimidates.","description":"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.","dates":{"release":"2009-01-01T00:00:00Z","publication":"2009 Sep","modification":"2025-04-04T00:07:29.99Z","creation":"2019-03-27T00:25:12Z"},"accession":"S-EPMC2748823","cross_references":{"pubmed":["19689147"],"doi":["10.1021/jo901109s"]}}