Dual functionalization of mesoporous organosilicon nanoflowers enhances heterogeneous chemoenzymatic conversion of alkynes toward enantiopure alcohols†

IF 9.3 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry Pub Date : 2025-07-02 DOI:10.1039/D5GC02373D

Chen Huang, Qian Zhang, Xiaoyang Yue, Aidang Lu, Guanhua Liu, Ying He, Li Ma, Liya Zhou, Yunting Liu and Yanjun Jiang

{"title":"Dual functionalization of mesoporous organosilicon nanoflowers enhances heterogeneous chemoenzymatic conversion of alkynes toward enantiopure alcohols†","authors":"Chen Huang, Qian Zhang, Xiaoyang Yue, Aidang Lu, Guanhua Liu, Ying He, Li Ma, Liya Zhou, Yunting Liu and Yanjun Jiang","doi":"10.1039/D5GC02373D","DOIUrl":null,"url":null,"abstract":"A tandem chemoenzymatic cascade for the direct synthesis of chiral alcohols from bulk alkynes is promising but challenging, as it couples the gold-catalysed alkyne hydration with an alcohol dehydrogenase-driven asymmetric reduction of the resulting ketones. Herewith two heterogeneous bifunctional catalysts are fabricated for chemocatalytic and biocatalytic steps, respectively. The bi-functionalized chemocatalyst (Au@HS/SO3H-DON), which possesses both Au NPs and Brønsted acid catalytic sites, exhibits superior catalytic performance and better reusability compared to those of homogeneous Au(III) catalysts. The bi-functionalized biocatalyst (ADH@QA-DON) exhibits enhanced reusability over free ADH and enriches NADH, enhancing the overall catalytic performance. Various chiral alcohols are directly obtained from alkynes with high yields (73%–92%) and enantioselectivity (>99% ee) via tandem cascade reactions catalyzed by bifunctional chemo- and biocatalysts. By fabricating a continuous-flow system, a space–time yield (STY) of 4.69 g L−1 h−1 for (S)-1-phenylethanol can be achieved, which is 6.7-fold higher than that obtained in batch.","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 29","pages":" 8858-8866"},"PeriodicalIF":9.3000,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Green Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/gc/d5gc02373d","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}

引用次数: 0

Abstract

A tandem chemoenzymatic cascade for the direct synthesis of chiral alcohols from bulk alkynes is promising but challenging, as it couples the gold-catalysed alkyne hydration with an alcohol dehydrogenase-driven asymmetric reduction of the resulting ketones. Herewith two heterogeneous bifunctional catalysts are fabricated for chemocatalytic and biocatalytic steps, respectively. The bi-functionalized chemocatalyst (Au@HS/SO₃H-DON), which possesses both Au NPs and Brønsted acid catalytic sites, exhibits superior catalytic performance and better reusability compared to those of homogeneous Au(III) catalysts. The bi-functionalized biocatalyst (ADH@QA-DON) exhibits enhanced reusability over free ADH and enriches NADH, enhancing the overall catalytic performance. Various chiral alcohols are directly obtained from alkynes with high yields (73%–92%) and enantioselectivity (>99% ee) via tandem cascade reactions catalyzed by bifunctional chemo- and biocatalysts. By fabricating a continuous-flow system, a space–time yield (STY) of 4.69 g L⁻¹ h⁻¹ for (S)-1-phenylethanol can be achieved, which is 6.7-fold higher than that obtained in batch.

Abstract Image

查看原文本刊更多论文

介孔有机硅纳米花的双功能化增强了炔烃向对映纯醇†的非均相化学酶转化

从大块炔直接合成手性醇的串联化学酶级联反应很有前景，但也很有挑战性，因为它将金催化的炔水合反应与醇脱氢酶驱动的酮的不对称还原结合在一起。本文分别制备了用于化学催化和生物催化的两种多相双功能催化剂。该双功能化化学催化剂（Au@HS/SO3H-DON）同时具有Au NPs和Brønsted酸性催化位点，与均相Au（III）催化剂相比，具有优异的催化性能和更好的可重复使用性。双功能化的生物催化剂（ADH@QA-DON）与游离的ADH相比具有更高的可重复使用性，并且富集了NADH，从而提高了整体的催化性能。通过双功能化学催化剂和生物催化剂催化的串联级联反应，直接从炔中获得了各种手性醇，收率高（73%-92%），对映选择性高（99% ee）。通过制造连续流系统，(S)-1-苯乙醇的空时产率（STY）为4.69 g L−1 h−1，比批量生产高出6.7倍。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Green Chemistry 化学-化学综合

CiteScore

16.10

自引率

7.10%

发文量

677

审稿时长

1.4 months

期刊介绍： Green Chemistry is a journal that provides a unique forum for the publication of innovative research on the development of alternative green and sustainable technologies. The scope of Green Chemistry is based on the definition proposed by Anastas and Warner (Green Chemistry: Theory and Practice, P T Anastas and J C Warner, Oxford University Press, Oxford, 1998), which defines green chemistry as the utilisation of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products. Green Chemistry aims to reduce the environmental impact of the chemical enterprise by developing a technology base that is inherently non-toxic to living things and the environment. The journal welcomes submissions on all aspects of research relating to this endeavor and publishes original and significant cutting-edge research that is likely to be of wide general appeal. For a work to be published, it must present a significant advance in green chemistry, including a comparison with existing methods and a demonstration of advantages over those methods.