2000
DOI: 10.1021/ja0000807
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Abstract: Many biological transformations are effected via electron transfer or homolytic bond cleavage, and thus proceed through radical mechanisms. 1 Early studies of the biosynthesis of immunodominant 3,6-dideoxyhexoses found in the lipopolysaccharide of several pathogenic bacterial strains, as exemplified by the biosynthesis of CDP-L-ascarylose (1) in Yersinia pseudotuberculosis V, have demonstrated that the C-3 deoxygenation step proceeds through a radical mechanism and requires a unique pair of enzymes, E 1 2 and … Show more

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Cited by 19 publications
(28 citation statements)
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“…[149] The first half of ColD catalysis was shown to mimic the E 1 reaction, with Schiff base formation and dehydration to give an intermediate similar to 143 (146, Scheme 11 g). The second half of the ColD reaction involves hydrolysis of the D 3, 4 -amino-mannoseen intermediate (146) to give PLP and an enamine sugar (147), which then undergoes tautomerization and subsequent hydrolysis to form the 4-keto-3,6-dideoxymannose product (148), releasing ammonia in the process. In contrast to the E 1 reaction, where PMP is regenerated by sequential one-electron reduc-tion from E 3 , the PMP coenzyme in ColD must be regenerated from PLP after each catalytic cycle by a transamination reaction in the presence of glutamate.…”
Section: Methylationmentioning
confidence: 99%
“…[149] The first half of ColD catalysis was shown to mimic the E 1 reaction, with Schiff base formation and dehydration to give an intermediate similar to 143 (146, Scheme 11 g). The second half of the ColD reaction involves hydrolysis of the D 3, 4 -amino-mannoseen intermediate (146) to give PLP and an enamine sugar (147), which then undergoes tautomerization and subsequent hydrolysis to form the 4-keto-3,6-dideoxymannose product (148), releasing ammonia in the process. In contrast to the E 1 reaction, where PMP is regenerated by sequential one-electron reduc-tion from E 3 , the PMP coenzyme in ColD must be regenerated from PLP after each catalytic cycle by a transamination reaction in the presence of glutamate.…”
Section: Methylationmentioning
confidence: 99%
“…Evidence of the existence of radical intermediates in E 1 was demonstrated experimentally using both EPR and ENDOR spectroscopic techniques [83,84]. This set of experiments revealed the presence of two radical species during turnover, one of which could be assigned to the flavin semiquinone radical.…”
Section: Deoxygenationmentioning
confidence: 99%
“…Purification by flash column chromatography (1:3 EtOAc in hexanes) yielded 2.41 g (88%) of 17 as a clear oil. 1 4.01 (dd, 1H, J = 3.6, 9.9 Hz), 3.88 (dq, 1H, J = 1.5, 6.6 Hz), 3.82 (dd, 1H, J = 3.6, 9.9 Hz), 3.68 (dd, 1H, J = 1.5, 3.6 Hz), 3.32 (s, 3H), 1.20 (d, 3H, J = 6.6 Hz); 13 …”
Section: Methyl 4-azido-23-di-o-benzyl-46-dideoxy-α-d-galactopyranomentioning
confidence: 99%