One pot chemo/enzymatic synthesis of chiral <strong>δ</strong>-substituent caprolactam and its configuration controlling

doi:10.3785/j.issn.1008-9497.2024.01.007

Journal of Zhejiang University (Science Edition)

2024, Vol. 51

Issue (1): 55-63 DOI: 10.3785/j.issn.1008-9497.2024.01.007

Chemistry

One pot chemo/enzymatic synthesis of chiral δ-substituent caprolactam and its configuration controlling

Meiling TU,Qining WANG,Yanjun LI,Jianting ZHANG,Jining JIA,Asan YANG

College of Chemical Engineering，Zhejiang University of Technology，Hangzhou 310014，China

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Abstract

Herein, a novel one pot synthesis of chiral δ-substituent caprolactam strategy which applies 1-substituent homoallylic amine as the starting material is reported. This method combines the enzymatic dynamic kinetic resolution (DKR) and ring cross metathesis. Moreover, the configuration of caprolactam can be controlled by using lipase and protease as the DKR catalyst. The enantiomeric excess value of obtained R- and S-caprolactam can reach up to 90% and 82%, the yield can also be above 82% and 70%.

Key words： chiral caprolactam configuration-controlling synthesis one pot chemo/enzymatic synthesis

Received: 19 August 2022 Published: 10 January 2024

CLC:

TQ 46

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	Meiling TU
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	Yanjun LI
	Jianting ZHANG
	Jining JIA
	Asan YANG

Cite this article:

Meiling TU,Qining WANG,Yanjun LI,Jianting ZHANG,Jining JIA,Asan YANG. One pot chemo/enzymatic synthesis of chiral δ-substituent caprolactam and its configuration controlling. Journal of Zhejiang University (Science Edition), 2024, 51(1): 55-63.

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https://www.zjujournals.com/sci/EN/Y2024/V51/I1/55

手性δ-取代己内酰胺化学/酶串联一锅法合成及立体构型调控

报道了一种以1-取代高烯丙基胺为原料，结合酶催化动态动力学拆分与分子内烯烃复分解反应串联一锅法制备手性δ-取代己内酰胺的方法。分别用脂肪酶和蛋白酶作为动态动力学拆分催化剂，实现了手性δ-取代己内酰胺立体构型的调控。通过该方法制备的R-δ-取代己内酰胺的对映体过量值（enantiomeric excess，ee）均在90%以上，产率维持在76%以上；所制备的S-δ-取代己内酰胺的ee也在82%以上，产率均高于70%。

关键词： 手性己内酰胺, 立体构型可调控合成, 化学/酶串联一锅法合成

Fig.1 Chemo-enzymatic synthesis of chiral δ-substituent caprolactam

Table 1 The results of enzymatic DKR of 1-phenylbut-3-en-1-amine

Table 2 Chemo-enzymatic synthesis of δ-caprolactam

Table 3 Chemo/enzymatic synthesis of chiral δ-substituent caprolactam


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