Characterization of Radical SAM Adenosylhopane Synthase, HpnH, which Catalyzes the 5'-Deoxyadenosyl Radical Addition to Diploptene in the Biosynthesis of C35 Bacteriohopanepolyols.,Angewandte Chemie International Edition

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Characterization of Radical SAM Adenosylhopane Synthase, HpnH, which Catalyzes the 5'-Deoxyadenosyl Radical Addition to Diploptene in the Biosynthesis of C35 Bacteriohopanepolyols.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2019-11-19 , DOI: 10.1002/anie.201911584
Shusuke Sato ₁ , Fumitaka Kudo ₁ , Michel Rohmer ₂ , Tadashi Eguchi ₁

Affiliation

Adenosylhopane is a crucial intermediate in the biosynthesis of bacteriohopanepolyols, which are widespread prokaryotic membrane lipids. Herein, it is demonstrated that reconstituted HpnH, a putative radical S-adenosyl-l-methionine (SAM) enzyme, commonly encoded in the hopanoid biosynthetic gene cluster, converts diploptene into adenosylhopane in the presence of SAM, flavodoxin, flavodoxin reductase, and NADPH. NMR spectra of the enzymatic reaction product were identical to those of synthetic (22R)-adenosylhopane, indicating that HpnH catalyzes stereoselective C-C formation between C29 of diploptene and C5' of 5'-deoxyadenosine. Further, the HpnH reaction in D2 O-containing buffer revealed that a D atom was incorporated at the C22 position of adenosylhopane. Based on these results, we propose a radical addition reaction mechanism catalyzed by HpnH for the formation of the C35 bacteriohopane skeleton.

中文翻译：

自由基SAM腺嘌呤合酶HpnH的表征，该酶催化5脱氧腺苷基向二氯丁烯中的自由基加成反应，可生物合成C35细菌-庚烷多元醇。

腺苷紫杉醇是细菌紫杉醇多元醇的生物合成中的关键中间体，而细菌紫杉醇多元醇是广泛的原核生物膜脂质。在此，证明了重组的HpnH（一种公认的自由基S-腺苷-1-甲硫氨酸（SAM）酶，通常在hopanoid生物合成基因簇中编码）在SAM，黄酮毒素，黄酮毒素还原酶和NADPH的存在下将二萜烯转化为腺苷。。酶促反应产物的NMR谱图与合成的（22R）-腺苷胆碱的谱图相同，表明HpnH催化双萜的C29和5'-脱氧腺苷的C5'之间的立体选择性CC形成。此外，在含D 2 O的缓冲液中的HpnH反应表明，在腺苷胆碱的C 22位上掺入了D原子。根据这些结果，

更新日期：2019-11-20

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