当前位置: X-MOL 学术Biochemistry › 论文详情
Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)
Stereospecific Formation of Z-Trisubstituted Double Bonds by the Successive Action of Ketoreductase and Dehydratase Domains from trans-AT Polyketide Synthases
Biochemistry ( IF 2.9 ) Pub Date : 2018-01-02 00:00:00 , DOI: 10.1021/acs.biochem.7b01253
Xinqiang Xie 1 , David E. Cane 1
Affiliation  

Incubation of (±)-2-methyl-3-ketobutyryl-SNAC (3) and (±)-2-methyl-3-ketopentanoyl-SNAC (4) with BonKR2 or OxaKR5, ketoreductase domains from the bongkrekic acid (1) and oxazolomycin (2) polyketide synthases, in the presence of NADPH gave in each case the corresponding (2R,3S)-2-methyl-3-hydroxybutyryl-SNAC (5) or (2R,3S)-2-methyl-3-hydroxypentanoyl-SNAC (6) products, as established by chiral gas chromatography–mass spectrometry analysis of the derived methyl esters. Identical results were obtained by BonKR2- and OxaKR5-catalyzed reduction of chemoenzymatically prepared (2R)-2-methyl-3-ketopentanoyl-EryACP6, (2R)-2-methyl-3-ketobutyryl-BonACP2 (12), and (2R)-2-methyl-3-ketopentanoyl-BonACP2 (13). The paired dehydratase domains, BonDH2 and OxaDH5, were then shown to catalyze the reversible syn dehydration of (2R,3S)-2-methyl-3-hydroxybutyryl-BonACP2 (14) to give the corresponding trisubstituted (Z)-2-methylbutenoyl-BonACP2 (16).

中文翻译:

通过反式-AT聚酮化合物合酶的酮还原酶和脱水酶结构域的连续作用,Z-三取代双键的立体特异性形成。

将(±)-2-甲基-3-酮丁酰基-SNAC(3)和(±)-2-甲基-3-酮戊酸-SNAC (4)与BonKR2或OxaKR5(来自邦克雷奇酸(1)和恶唑霉素(2)聚酮化合物合酶,在NADPH存在下,在每种情况下均给出相应的(2 R,3 S)-2-甲基-3-羟基丁酰基-SNAC(5)或(2 R,3 S)-2-甲基-3-羟基戊酰基-SNAC(6)产物,是通过对衍生的甲酯的手性气相色谱-质谱分析确定的。通过BonKR2-和OxaKR5-催化还原的化学酶法制备获得了相同的结果(2R)-2-甲基-3-酮戊基-EryACP6,(2 R)-2-甲基-3-酮丁酰基-BonACP2(12)和(2 R)-2-甲基-3-酮基戊基-BonACP2(13)。成对脱水酶结构域,BonDH2和OxaDH5,然后显示催化可逆顺式(2的脱水- [R,3小号)-2-甲基- 3-羟基丁BonACP2(14),以得到相应的三取代(Ž)-2-甲基丁烯酰-BonACP2(16)
更新日期:2018-01-02
down
wechat
bug