Regio- and Stereoselective Aliphatic-Aromatic Cross-Benzoin Reaction: Enzymatic Divergent Catalysis
Regio- and Stereoselective Aliphatic-Aromatic Cross-Benzoin Reaction: Enzymatic Divergent Catalysis
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DOI：
10.1002/chem.201602084
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发表时间：
2016-09-01
影响因子：
4.3
通讯作者：
Mueller, Michael
中科院分区：
文献类型：
--
作者：
Beigi, Maryam;Gauchenova, Ekaterina;Mueller, Michael
研究了荧光假单胞菌的苯甲醛裂解酶（PfBAL）、恶臭假单胞菌的苯甲酰甲酸脱羧酶（PpBFD-L461 A）、乳酸乳球菌的支链2-酮酸脱羧酶（LlKdcA）和巴氏醋酸杆菌的丙酮酸脱羧酶（ApPDC-E469 G）对手性2-羟基酮的催化不对称合成。从相同的底物组开始，取代的苯甲醛与不同的脂肪族醛组合，PfBAL和PpBFD-L461 A分别选择性地递送（R）-和（S）-2-羟基-苯丙酮衍生物。（R）和（S）-苯基乙酰基甲醇（1-羟基-1-苯基丙酮）衍生物可分别使用LlKdcA和ApPDC-E469 G以类似方式获得。在许多情况下，可以实现优异的立体化学纯度（>98%对映体过量）。因此，在不对称手性-芳香族交叉苯偶姻反应中产物的区域和立体化学可以仅通过选择适当的酶或酶变体来控制。
The catalytic asymmetric synthesis of chiral 2-hydroxy ketones by using different thiamine diphosphate dependent enzymes, namely benzaldehyde lyase from Pseudomonas fluorescens (PfBAL), a variant of benzoylformate decarboxylase from Pseudomonas putida (PpBFD-L461A), branched-chain 2-keto acid decarboxylase from Lactococcus lactis (LlKdcA) and a variant of pyruvate decarboxylase from Acetobacter pasteurianus (ApPDC-E469G), was studied. Starting with the same set of substrates, substituted benzaldehydes in combination with different aliphatic aldehydes, PfBAL and PpBFD-L461A selectively deliver the (R)-and (S)-2-hydroxy-propiophenone derivatives, respectively. The (R)and (S)-phenylacetylcarbinol (1-hydroxy-1-phenylacetone) derivatives are accessible in a similar way using LlKdcA and ApPDC-E469G, respectively. In many cases excellent stereochemical purities (>98% enantiomeric excess) could be achieved. Hence, the regio- and stereochemistry of the product in the asymmetric aliphatic-aromatic cross-benzoin reaction can be controlled solely by choice of the appropriate enzyme or enzyme variant.