Regiochemical control in the synthesis of tetrahydrofurans by acid- catalyzed cyclization of hydroxy selenides and hydroxy sulfides

Tetrahedron

Volumn 55, Issue 15, 1999, Pages 4769-4782

  Gruttadauria, Michelangelo ^a   Lo Meo, Paolo ^a   Noto, Renato ^a,b  

^a Dipto di Chim Organica E Paterno   (Italy)

^b ABDUS SALAM INTERNATIONAL CENTRE FOR THEORETICAL PHYSICS   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

2 BUTYL 5 HYDROXYMETHYL 3 PHENYLSELANYLTETRAHYROFURAN; 4 HYDROXY 2 (1' PHENYLSELANYLPENTYL)TETRAHYDROFURAN; SELENIDE; SULFIDE; TETRAHYDROFURAN DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CHEMICAL BOND; CHEMICAL REACTION KINETICS; CHEMICAL STRUCTURE; CONFORMATION; CONFORMATIONAL TRANSITION; CYCLIZATION; HYDROGENATION; PRIORITY JOURNAL; REACTION TIME; REDUCTION; STEREOCHEMISTRY; STRUCTURE ACTIVITY RELATION; SYNTHESIS;

EID: 0033537883     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4020(99)00149-0     Document Type: Article

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29. Semiempirical calculations with the AM1 method were also performed, but results are unsatisfactory. In fact, conformational analysis does not predict any stable "apt for closure" conformation corresponding to the endolexo product; moreover the method fails in the prediction of transition states energies, which do not match the experimental reactivity.
30. Comparison between models D and E shows that the TMS group lowers the activation energy. Nonetheless such an effect seems overestimated. As a matter of fact, the predicted activation energy for F, which is comparable with that for D, seems low in front of the experimental reactivity trend. Noticeably, calculations performed on the non-silylated analogue of F predict for the "endolexo" closure an activation energy of about 23 kcal/mol. For F and its non-silylated analogue, the predicted higher activation energy than E and D respectively, may be accounted for by a stabilizing effect of the benzyloxy group upon the positively charged episelenonium framework in the intermediate species.