PARALLELS AND DECISIVE DIFFERENCES IN VITAMIN-B12 BIOSYNTHESES

PARALLELS AND DECISIVE DIFFERENCES IN VITAMIN-B12 BIOSYNTHESES
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DOI:
10.1002/anie.199316511
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发表时间:
1993-11-01
影响因子:
16.6
通讯作者:
MULLER, G
MULLER, G
中科院分区:
化学1区
文献类型:
--
作者:
BLANCHE, F;THIBAUT, D;MULLER, G

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对微生物合成维生素B12的化学性质的研究[1.141]表明,需氧假单胞菌和厌氧菌谢尔曼丙酸杆菌的个别反应的组织结构有很大的不同,这些差异可能是起源于进化。Blanche,Crouzet等人的工作。LLA-CL提供了对维生素B合成的分子本质的深刻洞察。它们的构建和重组菌株的高效应用导致了新的和壮观的维生素B1前体的发现和分离。研究表明,通过前胡萝卜素2(1)和3(2)r2a、14I以及新发现的环收缩前胡萝卜素4(3)[31,6(4),[~]6y(5),i5‘和8~(6)[J(方案1)],在没有钴的情况下合成了四吡咯维生素B,配体氢比酸7I2]。在导致7-a,c-二胺的两个强制性酰化之后,[i钴被负责形成维生素Bi的钴络合酶插入。‘在P.shermanii的情况下,7和7-apdiamide都不是维生素Bi的前体[299a1而不是椰草酸],含钴的类似物7,和8-a,c-二胺出现在生物合成途径中。希尔曼巴氏杆菌的O1酶制剂不仅能在体外转化氧-2,而且还能在体外转化细菌。
Studies on the chemical nature of the microbial biosynthesis of vitamin B12 [1.141 have revealed that the organization of the individual reactions in the aerobe Pseudomonas denitriJicans and the anaerobe Propionibacterium shermanii differs significantly, and that these differences could be evolutionary in their origins. The work of Blanche, Crouzet et al. lla-cl has provided deep insight into the molecular nature of vitamin B,, synthesis. Their construction and efficient application of recombinant strains of P. denitrificans led to the discovery and isolation of new and spectacular vitamin B,, precursors with the responsible cloned enzymes.It was shown that the tetrapyrrolic vitamin B,, ligand hydrogenobyrinic acid 7I2] is synthesized without cobalt via the precorrins 2 (1) and 3 (2) r2a, l4I as well as the newly discovered ring-contracted precorrins 4 (3)[31, 6~(4),[~] 6y (5), I5'and 8~(6)[~ J (Scheme 1). After two obligatory amidations leading to 7-a, c-diamide,['I cobalt is inserted by the cobaltchelatase responsible for vitamin B,, formation."'In the case of P. shermanii neither 7 nor 7-apdiamide are precursors of vitamin B,,.[299a1 Instead cobyrinic acid@), the cobaltcontaining analogue of 7, and 8-a, c-diamide appear in the biosynthetic pathway.['". O1 Enzyme preparations from P. shermanii are able to transform in vitro not only the oxi-