Benzene-free synthesis of catechol: Interfacing microbial and chemical catalysis
Benzene-free synthesis of catechol: Interfacing microbial and chemical catalysis
复制标题
DOI：
10.1021/ja045148n
复制
发表时间：
2005-03-09
影响因子：
15
通讯作者：
Frost, JW
中科院分区：
文献类型：
--
作者：
Li, WS;Xie, DM;Frost, JW
芳烃的毒性常常限制其微生物合成的产率。例如，大肠杆菌WN 1/pWL1.290A在发酵罐控制条件下从葡萄糖合成邻苯二酚的5%产率反映了邻苯二酚的微生物毒性。使用原位树脂基提取来降低培养基中邻苯二酚的浓度，从而降低其在由葡萄糖通过E. coliWN 1/pWL1.290A，邻苯二酚得率为7%。然后探索微生物与化学合成的接口，其中葡萄糖被微生物转化为无毒中间体，然后将该中间体化学转化为邻苯二酚。检查的中间体包括3-脱氢奎尼酸、3-脱氢莽草酸和原儿茶酸。3-脱氢奎宁酸和3-脱氢莽草酸分别由E. coliOP1.1/pJY1.216A和EscherichiKL 3/pJY1.216A从葡萄糖中提取邻苯二酚，然后在290 ℃的水中反应，以葡萄糖为原料，总收率分别为10%和26%。随后通过在培养基中3-脱氢奎尼酸和3-脱氢莽草酸的高产化学脱水，然后提取所得的原儿茶酸，来避免从培养基中提取这些儿茶酚前体的问题。原儿茶酸酯在290 ℃的水中反应后，葡萄糖经3-脱氢奎尼酸酯化学脱水和3-脱氢莽草酸酯化学脱水合成邻苯二酚的总收率分别为25%和30%。利用E. coli KL 3/pWL 2.46B，经提取、脱羧得到邻苯二酚，总收率为24%。采用树脂法原位提取E. coliKL 3/pWL2.46B，然后检测该儿茶酚前体的化学脱羧。采用这两种策略来处理芳香族产物的微生物毒性导致了最高的总产率，其中从葡萄糖以43%的总产率合成邻苯二酚。
The toxicity of aromatics frequently limits the yields of their microbial synthesis. For example, the 5% yield of catechol synthesized from glucose by Escherichia coli WN1/pWL1.290A under fermentor-controlled conditions reflects catechol's microbial toxicity. Use of in situ resin-based extraction to reduce catechol's concentration in culture medium and thereby its microbial toxicity during its synthesis from glucose by E. coli WN1/pWL1.290A led to a 7% yield of catechol. Interfacing microbial with chemical synthesis was then explored where glucose was microbially converted into a nontoxic intermediate followed by chemical conversion of this intermediate into catechol. Intermediates examined include 3-dehydroquinate, 3-dehydroshikimate, and protocatechuate. 3-Dehydroquinate and 3-dehydroshikimate synthesized, respectively, by E. coli OP1.1/pJY1.216A and E coli KL3/pJY1.216A from glucose were extracted and then reacted in water heated at 290degreesC to afford catechol in overall yields from glucose of 10% and 26%, respectively. The problematic extraction of these catechol precursors from culture medium was subsequently circumvented by high-yielding chemical dehydration of 3-dehydroquinate and 3-dehydroshikimate in culture medium followed by extraction of the resulting protocatechuate. After reaction of protocatechuate in water heated at 290degreesC, the overall yields of catechol synthesized from glucose via chemical dehydration of 3-dehydroquinate and chemical dehydration of 3-dehydroshikimate were, respectively, 25% and 30%. Direct synthesis of protocatechuate from glucose using E. coli KL3/pWL2.46B followed by its extraction and chemical decarboxylation in water gave a 24% overall yield of catechol from glucose. In situ resin-based extraction of protocatechaute synthesized by E. coli KL3/pWL2.46B followed by chemical decarboxylation of this catechol percursor was then examined. This employment of both strategies for dealing with the microbial toxicity of aromatic products led to the highest overall yield with catechol synthesized in 43% overall yield from glucose.