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Volumn 13, Issue 19, 2007, Pages 5566-5584

First synthesis of 2'-deoxyfluoropuromycin analogues: Experimental insight into the mechanism of the staudinger reaction

Author keywords

Antibiotics; Antitumor agents; Azides; Nucleotides; Staudinger vilarrasa; Triazenes

Indexed keywords

DINUCLEOTIDYL AZIDE; NITRITE-ASSISTED FORMATION; SODIUM AZIDE; STAUDINGER REACTION;

EID: 34547222547     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200700058     Document Type: Article
Times cited : (29)

References (165)
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    • 2O, respectively, to give esters R-O-C(O)R' and, concomitantly, acids HO-C(O)R' and alkenes derived from R. Extensive kinetic studies on the reaction of N-alkyl-W-nitrosoamides identified a firstorder rate-determining step, which could only be explained through the initial relatively slow formation of a four-membered R-N=JV-OC(O)R' ring (N-C connected), described as a concerted intramolecular N,O-acyl shift,...
    • 2O, respectively, to give esters R-O-C(O)R' and, concomitantly, acids HO-C(O)R' and alkenes derived from R. Extensive kinetic studies on the reaction of N-alkyl-W-nitrosoamides identified a firstorder rate-determining step, which could only be explained through the initial relatively slow formation of a four-membered R-N=JV-OC(O)R' ring (N-C connected), described as a concerted intramolecular N,O-acyl shift, followed by another 1,3-shift of the R group from N to O to give the ester and dinitrogen or, alternatively, the elimination of R to give the acid, dinitrogen and the alkene. Today's credo seems to be (for some of vis) that four-membered ring transition states, in order to be sufficiently stable, necessitate at least one at least third-row element in the ring, like in a Wittig or azaWittig reaction.


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