PQQ‐dependent Dehydrogenase Enables One‐pot Bi‐enzymatic Enantio‐convergent Biocatalytic Amination of Racemic sec‐Allylic Alcohols,ChemCatChem

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PQQ‐dependent Dehydrogenase Enables One‐pot Bi‐enzymatic Enantio‐convergent Biocatalytic Amination of Racemic sec‐Allylic Alcohols
ChemCatChem ( IF 3.8 ) Pub Date : 2020-11-27 , DOI: 10.1002/cctc.202001707
Somayyeh Gandomkar ₁ , Raquel Rocha ₁ , Frieda A Sorgenfrei _{1,

2} , Lía Martínez Montero ₁ , Michael Fuchs ₁ , Wolfgang Kroutil _{1,

3,

4}

Affiliation

The asymmetric amination of secondary racemic allylic alcohols bears several challenges like the reactivity of the bi‐functional substrate/product as well as of the α,β‐unsaturated ketone intermediate in an oxidation‐reductive amination sequence. Heading for a biocatalytic amination cascade with a minimal number of enzymes, an oxidation step was implemented relying on a single PQQ‐dependent dehydrogenase with low enantioselectivity. This enzyme allowed the oxidation of both enantiomers at the expense of iron(III) as oxidant. The stereoselective amination of the α,β‐unsaturated ketone intermediate was achieved with transaminases using 1‐phenylethylamine as formal reducing agent as well as nitrogen source. Choosing an appropriate transaminase, either the (R)‐ or (S)‐enantiomer was obtained in optically pure form (>98 % ee). The enantio‐convergent amination of the racemic allylic alcohols to one single allylic amine enantiomer was achieved in one pot in a sequential cascade.

中文翻译：

PQQ 依赖性脱氢酶可实现外消旋仲烯丙醇的一锅双酶对映异构体生物催化胺化

仲外消旋烯丙醇的不对称胺化面临着一些挑战，例如双功能底物/产物以及氧化还原胺化序列中α,β-不饱和酮中间体的反应性。为了使用最少数量的酶进行生物催化胺化级联，氧化步骤依赖于具有低对映选择性的单一 PQQ 依赖性脱氢酶来实现。这种酶可以氧化两种对映体，但需要铁 (III) 作为氧化剂。使用1-苯乙胺作为形式还原剂以及氮源，通过转氨酶实现了α,β-不饱和酮中间体的立体选择性胺化。选择合适的转氨酶，可以获得光学纯形式的 ( R )-或 ( S )-对映体 (>98% ee )。外消旋烯丙醇对映收敛胺化为一种单一烯丙胺对映体，是在连续级联的一锅中实现的。

更新日期：2020-11-27

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