1356965-80-4Relevant academic research and scientific papers
Br?nsted Acid-Catalyzed Intramolecular Nucleophilic Substitution of the Hydroxyl Group in Stereogenic Alcohols with Chirality Transfer
Bunrit, Anon,Dahlstrand, Christian,Olsson, Sandra K.,Srifa, Pemikar,Huang, Genping,Orthaber, Andreas,Sj?berg, Per J. R.,Biswas, Srijit,Himo, Fahmi,Samec, Joseph S. M.
supporting information, p. 4646 - 4649 (2015/04/27)
The hydroxyl group of enantioenriched benzyl, propargyl, allyl, and alkyl alcohols has been intramolecularly displaced by uncharged O-, N-, and S-centered nucleophiles to yield enantioenriched tetrahydrofuran, pyrrolidine, and tetrahydrothiophene derivatives with phosphinic acid catalysis. The five-membered heterocyclic products are generated in good to excellent yields, with high degree of chirality transfer, and water as the only side-product. Racemization experiments show that phosphinic acid does not promote SN1 reactivity. Density functional theory calculations corroborate a reaction pathway where the phosphinic acid operates as a bifunctional catalyst in the intramolecular substitution reaction. In this mechanism, the acidic proton of the phosphinic acid protonates the hydroxyl group, enhancing the leaving group ability. Simultaneously, the oxo group of phosphinic acid operates as a base abstracting the nucleophilic proton and thus enhancing the nucleophilicity. This reaction will open up new atom efficient techniques that enable alcohols to be used as nucleofuges in substitution reactions in the future.
Phosphorothioic acids and related compounds as surrogates for H 2S-synthesis of chiral tetrahydrothiophenes
Robertson, Forest J.,Wu, Jimmy
supporting information; experimental part, p. 2775 - 2780 (2012/03/22)
The convenient preparation of chiral tetrahydrothiophenes (THTs) in high enantiopurity via phosphorothioic acids and related compounds is reported. We consider these to be safer alternatives to the use of H2S which is a highly toxic gas. Each o
