Department of Biotechnology, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan.
Plant Cell. 2011 Nov;23(11):4112-23. doi: 10.1105/tpc.110.082685. Epub 2011 Nov 29.
Glycyrrhizin, a triterpenoid saponin derived from the underground parts of Glycyrrhiza plants (licorice), has several pharmacological activities and is also used worldwide as a natural sweetener. The biosynthesis of glycyrrhizin involves the initial cyclization of 2,3-oxidosqualene to the triterpene skeleton β-amyrin, followed by a series of oxidative reactions at positions C-11 and C-30, and glycosyl transfers to the C-3 hydroxyl group. We previously reported the identification of a cytochrome P450 monooxygenase (P450) gene encoding β-amyrin 11-oxidase (CYP88D6) as the initial P450 gene in glycyrrhizin biosynthesis. In this study, a second relevant P450 (CYP72A154) was identified and shown to be responsible for C-30 oxidation in the glycyrrhizin pathway. CYP72A154 expressed in an engineered yeast strain that endogenously produces 11-oxo-β-amyrin (a possible biosynthetic intermediate between β-amyrin and glycyrrhizin) catalyzed three sequential oxidation steps at C-30 of 11-oxo-β-amyrin supplied in situ to produce glycyrrhetinic acid, a glycyrrhizin aglycone. Furthermore, CYP72A63 of Medicago truncatula, which has high sequence similarity to CYP72A154, was able to catalyze C-30 oxidation of β-amyrin. These results reveal a function of CYP72A subfamily proteins as triterpene-oxidizing enzymes and provide a genetic tool for engineering the production of glycyrrhizin.
甘草酸是从甘草植物(甘草)地下部分提取的三萜皂苷,具有多种药理活性,也被全世界用作天然甜味剂。甘草酸的生物合成涉及 2,3-氧化鲨烯初始环化为三萜骨架β-香树脂醇,然后在 C-11 和 C-30 位置进行一系列氧化反应,并在 C-3 羟基上进行糖基转移。我们之前报道了鉴定一种细胞色素 P450 单加氧酶(P450)基因,该基因编码β-香树脂醇 11-氧化酶(CYP88D6),作为甘草酸生物合成中最初的 P450 基因。在这项研究中,鉴定了第二个相关的 P450(CYP72A154),并表明其负责甘草酸途径中的 C-30 氧化。在工程酵母菌株中表达的 CYP72A154 能够催化原位提供的 11-氧-β-香树脂醇(β-香树脂醇和甘草酸之间可能的生物合成中间体)的 C-30 上的三个连续氧化步骤,产生甘草次酸,一种甘草酸苷元。此外,与 CYP72A154 具有高度序列相似性的 Medicago truncatula 的 CYP72A63 能够催化 β-香树脂醇的 C-30 氧化。这些结果揭示了 CYP72A 亚家族蛋白作为三萜类氧化酶的功能,并为工程化生产甘草酸提供了遗传工具。