Ab Initio Study of the Thio-Ene Reaction. 1. The Enophile Substituent Effect

Bachrach, Steven M.; Jiang, Sulin

doi:10.1021/jo970608z

Cited by 9 publications

(2 citation statements)

References 35 publications

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“…In anhydrous acetonitrile, complete selectivity for thioester formation was obtained with diazo compound 2 (Scheme 3). This selectivity rules out a cyclic transition state reminiscent of an ene reaction, 36,37 which would provide the thionoester as the product. On the other hand, diazo compound 1 produced a mixture of thio-and thionoester products.…”

Section: Resultsmentioning

confidence: 98%

Diazo compounds for the bioreversible esterification of proteins

et al. 2015

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A diazo compound is shown to convert carboxylic acids to esters efficiently in an aqueous environment. The basicity of the diazo compound is critical: low basicity does not lead to a reaction but high basicity leads to hydrolysis. This reactivity extends to carboxylic acid groups in a protein. The ensuing esters are hydrolyzed by human cellular esterases to regenerate protein carboxyl groups. This new mode of chemical modification could enable the key advantages of prodrugs to be translated from small-molecules to proteins.

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Section: Resultsmentioning

confidence: 98%

Diazo compounds for the bioreversible esterification of proteins

et al. 2015

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“…We have long been interested in pericyclic reactions of heterosystems. − In this paper, we report a theoretical examination of the Diels−Alder reaction of a series of substituted CSe systems. We find that substituent effects conform to the standard FMO model.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study of the Diels−Alder Reaction of Selenoaldehydes and Selenoketones

Bachrach

Jiang

1999

J. Org. Chem.

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The Diels-Alder reaction of a series of substituted selenoaldehydes (Se=CHR; R = H, F, Me, OMe, CH(2)F, CF(3), and CN) or selenoketones (Se=CR(2); R = Me and CN) with 1,3-butadiene or 2-methoxy-1,3-butadiene to yield 3,6-dihydro-2H-selenopyrans were examined using B3LYP with a modified 6-31G basis set. This method is compared with results from a number of standard ab initio procedures and compares well with post-HF results. The Diels-Alder reaction of the selenocarbonyl compounds proceeds through a concerted, though asynchronous, transition state. Strong electron-withdrawing groups alter the mechanism; a charge-transfer complex is first formed, followed by a concerted TS before reaching the heterocyclic product. The transition state geometry, regiochemistry, and dependence of the activation barrier on substituents can be understood in terms of FMO theory.

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