Green Synthesis and Catalysis最新文献_第7页

Modulating regioselectivity of CYP107J3-catalyzed isophorone hydroxylation by disrupting the hydrophobic balance of the substrate binding pocket 通过破坏底物结合袋的疏水平衡调节 CYP107J3 催化的异佛尔酮羟基化的区域选择性

Green Synthesis and Catalysis Pub Date : 2024-05-31 DOI: 10.1016/j.gresc.2024.05.007

Meng Dai, Xiaojuan Yu, Xiaogang Peng, Zhiyong Guo, Huili Yu, Aitao Li

{"title":"Modulating regioselectivity of CYP107J3-catalyzed isophorone hydroxylation by disrupting the hydrophobic balance of the substrate binding pocket","authors":"Meng Dai, Xiaojuan Yu, Xiaogang Peng, Zhiyong Guo, Huili Yu, Aitao Li","doi":"10.1016/j.gresc.2024.05.007","DOIUrl":"https://doi.org/10.1016/j.gresc.2024.05.007","url":null,"abstract":"4-Hydroxyisophorone (4HIP) is an oxygenated intermediate derived from isophorone, serving as an important flavor and fragrance and chiral synthon of pharmaceutical drugs. In this study, a newly identified P450CYP107J3 from was found to prefer 4-hydroxylation of isophorone (80% regioselectivity) with 4HIP as the predominant product (59% product proportion). Bioinformatic analyses, including homologous modelling and molecular docking, reveal that four potential “hotspot” residues (L98, T300, M401 and V296) located on both sides of the substrate in the active pocket may control regioselectivity. By introducing polar residues to these hotspots to disrupt the hydrophobic balance, significant improvement in C4-regioselectivity was achieved by variants of L98, T300, and M401, with the most effective L98N exhibiting a notable enhancement of 93% C4-regioselectivity including 81% of 4HIP. Following, the double mutant L98N-M401F further improved both C4-regioselectivity (97%) and the proportion of 4HIP (86%). Remarkably, variant V296T essentially shifted regioselectivity from 4HIP to 6-hydroxyisophorone (6HIP) with an 80% preference for the latter, indicating the crucial role of V296 in controlling regioselectivity. Subsequently, the mechanism of regioselectivity of isophorone hydroxylation catalyzed by CYP107J3 was revealed by computational analysis. Furthermore, we demonstrated the generality of conserved hotspots L98 and V296 in mediating regioselectivity control in the CYP107J family members like CYP107J1 and CYP107J5. Overall, our study not only expands the biocatalytic toolbox for producing 4HIP and the -hydroxy ketone 6HIP but also provides efficient engineering strategy and knowledge for the regioselectivity control of P450s in potential applications.","PeriodicalId":12794,"journal":{"name":"Green Synthesis and Catalysis","volume":"81 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141885091","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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Catalyst-free electrochemical dearomatization of pyridine derivatives 吡啶衍生物的无催化剂电化学脱芳烃反应

Green Synthesis and Catalysis Pub Date : 2024-05-01 DOI: 10.1016/j.gresc.2022.06.006

Kui Wang , Yingjun Tian , Baoying Li , Ling Wang , Wei Gao , Xiaofei Jia , Ruiming Wang , Yanping Zhu , Jianbin Chen

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Cascade reaction of 3-formylchromones: Highly selective synthesis of 4-oxo-3-(1H-pyrrol-3-yl)-4H-chromenes 3- 甲酰基色素的级联反应：高选择性合成 4-氧代-3-(1H-吡咯-3-基)-4H-色烯

Green Synthesis and Catalysis Pub Date : 2024-05-01 DOI: 10.1016/j.gresc.2022.10.003

Ying Lv, Li Chen, Xinghan Yun, Kun Li, Shengjiao Yan

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Chemoselective synthesis of α-carboline derivatives via hypervalent iodine-catalyzed [3+3] annulation under metal-free conditions 在无金属条件下通过高价碘催化 [3+3] 环化化学选择性合成 α-咔啉衍生物

Green Synthesis and Catalysis Pub Date : 2024-05-01 DOI: 10.1016/j.gresc.2023.01.002

Shuowen Wang , Rong Li , Shanping Chen , Guojiang Mao , Wen Shao , Guo-Jun Deng

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Rh(II) catalyzed efficient sigmatropic rearrangement reaction of pyridotriazoles and sulfides Rh(II)催化吡啶三唑和硫化物的高效西格玛重排反应

Green Synthesis and Catalysis Pub Date : 2024-05-01 DOI: 10.1016/j.gresc.2023.04.004

Yuting Chen , Guanghui Lv , Zhiyang Li , Meiling Ye , Tianle Huang , Li Hai , Yong Wu

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Photochemical nitrene transfer reactions of iminoiodinanes with sulfoxides 亚氨基碘烷与硫氧化物的光化学芘转移反应

Green Synthesis and Catalysis Pub Date : 2024-05-01 DOI: 10.1016/j.gresc.2024.05.001

Xuemei Zhao, Zhiyuan Tang, Linlin Shi, Yujing Guo, Rene M. Koenigs, Xinqi Hao

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Direct C(sp3)-H functionalization with thiosulfonates via photoredox catalysis 通过光氧化催化实现硫代磺酸盐与 C(sp3)-H 的直接官能化

Green Synthesis and Catalysis Pub Date : 2024-05-01 DOI: 10.1016/j.gresc.2024.05.003

Linfeng Liu, Yujian Pang, Canliang Ma, Daiqing Zhou, Wenjie Zhang, Jin Huang, Jie Sun, Jiangkai Qiu, Yihuan Liu, Lei Shen, Zhenjiang Li, Kai Guo

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Ir-catalyzed photoredox cascade radical annulation reactions toward phosphinimides bearing quaternary carbon center at room temperature 室温下铱催化光氧化级联自由基环化反应生成含季碳中心的膦酰亚胺

Green Synthesis and Catalysis Pub Date : 2024-05-01 DOI: 10.1016/j.gresc.2024.04.006

Shujuan Xu, Fang Xun, Jiapian Huang, Jie Wu, Zhiyuan Chen

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Biocatalytic stereoselective synthesis of methyl mandelates by engineering a cytochrome P450 hydroxylase 通过细胞色素 P450 羟化酶的生物催化立体选择性合成扁桃酸甲酯

Green Synthesis and Catalysis Pub Date : 2024-05-01 DOI: 10.1016/j.gresc.2023.01.005

Lingzhi Xie , Yun Zhang , Ruyue Zhang , Haibo Cui , Baodong Cui , Wenyong Han , Nanwei Wan , Zhi Li , Yongzheng Chen

{"title":"Biocatalytic stereoselective synthesis of methyl mandelates by engineering a cytochrome P450 hydroxylase","authors":"Lingzhi Xie , Yun Zhang , Ruyue Zhang , Haibo Cui , Baodong Cui , Wenyong Han , Nanwei Wan , Zhi Li , Yongzheng Chen","doi":"10.1016/j.gresc.2023.01.005","DOIUrl":"10.1016/j.gresc.2023.01.005","url":null,"abstract":"<div><p>Chiral methyl mandelates are useful synthons in organic transformation and pharmaceutical synthesis. Green synthesis of these valuable compounds by direct C–H activating oxidative hydroxylation has attracted keen interest. Described herein is achieving the stereoselective and efficient bio-hydroxylation of methyl 2-phenylacetates to the chiral methyl mandelates by directed evolution of the cytochrome P450DA hydroxylase. In the present study, a new colorimetric high-throughput screening assay was successfully developed based on a dual-enzyme cascade for the engineering of the P450DA's hydroxylation activity. Several beneficial variants with enhanced bio-hydroxylation activity were created by combining random mutagenesis and site-saturated/directed mutagenesis strategies. Whole-cell bio-hydroxylation of various methyl 2-phenylacetates using the best septuplet-mutant P450DA-11 yielded the corresponding chiral methyl mandelates in up to 92% isolated yields and >99% <em>ee</em>.</p></div>","PeriodicalId":12794,"journal":{"name":"Green Synthesis and Catalysis","volume":"5 2","pages":"Pages 88-93"},"PeriodicalIF":0.0,"publicationDate":"2024-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666554923000054/pdfft?md5=8b25d52d413e20f9e147427b5b961e35&pid=1-s2.0-S2666554923000054-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87468871","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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Asymmetric reduction of conjugated CC bonds by immobilized fusion of old yellow enzyme and glucose dehydrogenase 通过固定融合老黄酶和葡萄糖脱氢酶不对称还原共轭 CC 键

Green Synthesis and Catalysis Pub Date : 2024-05-01 DOI: 10.1016/j.gresc.2022.10.012

Yongxing Li , Pengqian Luan , Lele Dong , Jianqiao Liu , Luying Jiang , Jing Bai , Fufeng Liu , Yanjun Jiang

{"title":"Asymmetric reduction of conjugated CC bonds by immobilized fusion of old yellow enzyme and glucose dehydrogenase","authors":"Yongxing Li , Pengqian Luan , Lele Dong , Jianqiao Liu , Luying Jiang , Jing Bai , Fufeng Liu , Yanjun Jiang","doi":"10.1016/j.gresc.2022.10.012","DOIUrl":"https://doi.org/10.1016/j.gresc.2022.10.012","url":null,"abstract":"<div><p>Asymmetric reduction of the conjugated C<img>C bonds by the old yellow enzymes (OYEs) presents a promising field in the synthesis of chiral chemicals. Nevertheless, few natural OYEs have been applied in large-scale applications due to the requirement of costly NADPH and low operational stability. Herein, a stable and efficient fusion of YqjM from <em>Bacillus subtilis</em> and glucose dehydrogenase (GDH) from <em>Bacillus megaterium</em> was constructed to stereoselectively reduce the conjugated C<img>C bonds in a self-sufficient continuous process. The effects of the enzyme order and different linkers on the fusions were investigated by structural analysis and all-atom molecular dynamics simulation. The best fusion YqjM_G_GDH gave 98% conversion of 100 mmol/L 2-methylcyclopentenone with an excellent <em>ee</em> value (>99%) in 3 h, while the mixture of individual enzymes only obtained 68% conversion after more than 8 h. The improved substrate conversion of YqjM_G_GDH fusion was probably attributed to the increased flexibility of each fused enzyme and the shortening of the diffusion distance of NADPH regenerated. A one-pot process was designed to purify and immobilize the fusion on the Ni<sup>2+</sup>-nitrilotriacetic acid functionalized magnetic mesoporous silica nanoflowers. The resulting immobilized biocatalyst not only catalyzed the asymmetric reduction of various <em>α,β</em>-unsaturated ketones (20 mmol/L) continuously with only 50 μmol/L NADP<sup>+</sup> to initiate the whole process, but also retained more than 82% of the initial activity after seven cycles, serving as a good candidate for the industrial applications.</p></div>","PeriodicalId":12794,"journal":{"name":"Green Synthesis and Catalysis","volume":"5 2","pages":"Pages 80-87"},"PeriodicalIF":0.0,"publicationDate":"2024-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666554922001119/pdfft?md5=e72d818078f5545af9df52bf008b7cf4&pid=1-s2.0-S2666554922001119-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141089938","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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