Green Chemistry最新文献

英文中文

Mild aqueous metal catalyzed oxidative conversion of low-density polyethylene to low molecular weight aliphatic carboxylic acids† 温和水性金属催化低密度聚乙烯与低分子量脂肪族羧酸的氧化转化†。

IF 9.3 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2024-10-04 DOI: 10.1039/D4GC02187H

Oleg Davydovich, Hemant Choudhary, Daniella V. Martinez, Jay E. Salinas, Estevan J. Martinez, Ryan D. Davis, Nathan R. Bays, David P. Schafer and Michael S. Kent

Aqueous oxidative deconstruction of low-density polyethylene (LDPE) was investigated using homogeneous first-row transition metal catalysts under mild conditions (130–150 °C and ≤100 PSI oxygen pressure). Oxidation of LDPE resulted in high yields of low molecular weight carboxylic acids (up to 75% yield as determined by carbon balance). Aqueous processing is well-suited for biological conversion of the breakdown products.

在温和的条件下（130-150 °C，≤100 PSI 氧压），使用均相第一排过渡金属催化剂研究了低密度聚乙烯（LDPE）的水氧化解构。低密度聚乙烯的氧化反应产生了高产率的低分子量羧酸（根据碳平衡测定，产率高达 75%）。水处理非常适合于分解产物的生物转化。

引用次数: 0

Chemodivergent alkylation of trifluoromethyl alkenes via photocatalytic coupling with alkanes. 通过光催化与烷烃偶联实现三氟甲基烯的化学歧化烷基化。

IF 9.3 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2024-10-04 DOI: 10.1039/d4gc04176c

Pol Martínez-Balart, Álvaro Velasco-Rubio, Sergio Barbeira-Arán, Hugo Jiménez-Cristóbal, Martín Fañanás-Mastral

gem-Difluoroalkenes and trifluoromethyl alkanes are prominent structures in biologically active compounds. Radical alkylation of α-trifluoromethyl alkenes represents a useful strategy to access these structures. However, reported methods have relied on the use of pre-functionalized radical precursors and examples involving the use of simple hydrocarbons as coupling partners are elusive. Here we report a chemodivergent methodology based on the direct activation of C(sp³)-H bonds enabled by HAT photoredox catalysis. This protocol provides an efficient platform for preparing both gem-difluoroalkenes and trifluoromethyl alkanes from ubiquitous hydrocarbon feedstocks, including gaseous alkanes. Importantly, chemoselectivity is easily achieved by simple modification of reaction conditions and/or additives.

gem-二氟烯烃和三氟甲基烷烃是生物活性化合物中的重要结构。α-三氟甲基烯的自由基烷基化是获得这些结构的有效策略。然而，已报道的方法都依赖于使用预官能化的自由基前体，而使用简单碳氢化合物作为偶联剂的例子却很难找到。在此，我们报告了一种基于 HAT 光氧化催化直接活化 C（sp3）-H 键的化学变异方法。该方法为从包括气态烷烃在内的各种烃类原料中制备二氟烯烃和三氟甲基烷烃提供了一个高效平台。重要的是，只需简单改变反应条件和/或添加剂，就能轻松实现化学选择性。

引用次数: 0

Poly(carbonate acetal) vitrimers with enhanced thermal properties and closed-loop thermal recyclability derived from waste polycarbonate-derived polyaldehyde and pentaerythritol/erythritol/d-sorbitol† 从废弃聚碳酸酯衍生的聚醛和季戊四醇/赤藓糖醇/山梨醇中提取的具有更强热性能和闭环热循环能力的聚碳酸酯缩醛玻璃体

IF 9.3 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2024-09-30 DOI: 10.1039/d4gc02934h

We synthesized three poly(carbonate acetal) vitrimers (PCA-P, PCA-E, PCA-S) by condensing a waste polycarbonate-derived polyaldehyde (WPC-CHO) with pentaerythritol, erythritol, and d-sorbitol, using 0.5–4.0 mol% p-toluene sulfonic acid (pTSA) as a catalyst. Flexible PCA films emerged at pTSA concentrations ≥1 mol%, indicating a critical threshold of acid for effective condensation. The glass transition temperatures (T_g) of the films remained consistent across pTSA concentrations but varied based on the multi-alcohol structure, with T_g values of 178 °C for both PCA-P and PCA-S, and 142 °C for PCA-E, suggesting superior performance of pentaerythritol and d-sorbitol over erythritol as building blocks. Among these, the PCA-S series exhibited the best performance and utilized the least expensive starting materials, achieving the highest cost-performance index. The PCAs, featuring covalent adaptable polyacetal networks, facilitated thermal reprocessing through acetal metathesis. The second reprocessed PCA-P and PCA-S maintained similar thermal and mechanical properties to their original forms, demonstrating a closed-loop recycling. These polymers showed stability in THF/H₂O (4/1) with 0.1–1.0 M H₂SO₄ at 25 °C, but can be degraded at 50 °C within 5 hours in both 0.5 M H₂SO₄ and HCl THF/H₂O (4/1) solutions. NMR analysis of the degraded PCA-P confirmed the recovery of WPC-CHO and pentaerythritol. Furthermore, PCA-based carbon-fiber-reinforced plastics (CFRPs) were prepared, and the carbon fibers were successfully recovered after acid degradation without any loss to their structural or tensile integrity.

我们使用 0.5-4.0 mol% 的对甲苯磺酸（pTSA）作为催化剂，通过将废弃聚碳酸酯衍生聚醛（WPC-CHO）与季戊四醇、赤藓糖醇和 D-山梨醇缩合，合成了三种聚（碳酸酯缩醛）玻璃体（PCA-P、PCA-E 和 PCA-S）。当 pTSA 浓度≥1 摩尔% 时，就会出现柔韧的 PCA 薄膜，这表明有效缩合的酸临界值很高。不同 pTSA 浓度下薄膜的玻璃化转变温度（Tg）保持一致，但根据多元醇结构的不同而有所不同，PCA-P 和 PCA-S 的 Tg 值均为 178 ℃，而 PCA-E 的 Tg 值为 142 ℃，这表明季戊四醇和 D-山梨醇作为构建模块的性能优于赤藓糖醇。其中，PCA-S 系列性能最佳，使用的起始材料成本最低，性价比指数最高。PCA 具有共价适应性聚缩醛网络，可通过缩醛偏聚作用进行热再加工。第二次再加工后的 PCA-P 和 PCA-S 保持了与其原始形态相似的热性能和机械性能，实现了闭环循环。这些聚合物在 25 °C、含 0.1-1.0 M H2SO4 的 THF/H2O (4/1) 溶液中表现出稳定性，但在 50 °C、含 0.5 M H2SO4 和 HCl 的 THF/H2O (4/1) 溶液中 5 小时内即可降解。对降解后的 PCA-P 进行核磁共振分析，证实了 WPC-CHO 和季戊四醇的回收。此外，还制备了基于 PCA 的碳纤维增强塑料 (CFRP)，碳纤维在酸降解后成功恢复，其结构和拉伸完整性没有受到任何影响。

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引用次数: 0

Enantioselective electrosynthesis of inherently chiral calix[4]arenes via a cobalt-catalyzed aryl C–H acyloxylation† 通过钴催化芳基 C-H 乙酰氧基化实现固有手性钙[4]炔的对映选择性电合成

IF 9.3 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2024-09-30 DOI: 10.1039/d4gc02877e

Inherently chiral calixarenes are known to exhibit versatile functions due to their delicate three-dimensional macrocyclic frameworks. However, the catalytic asymmetric synthesis of these compounds remains largely unexplored and poses a significant challenge. Herein, we report an unprecedented enantioselective electrochemical synthesis of inherently chiral calix[4]arenes. Our approach is based on a 3d metal cobalt-catalyzed asymmetric C–H acyloxylation of the prochiral macrocyclic frameworks. The easily accessible and modifiable chiral salicyloxazoline (Salox) was used as the ligand to efficiently regulate the enantioselectivity. This protocol proceeded smoothly under electrochemically mild conditions and was compatible with a wide range of carboxylic acids, including aryl carboxylic acids and tertiary, secondary, primary aliphatic carboxylic acids, yielding a variety of acyloxylated calix[4]arenes with good yields (up to 94% yield) and excellent enantioselectivities (95–99% ee). The synthetic practicability of this method was demonstrated by the scale-up reaction and the divergent derivatizations of the inherently chiral macrocyclic products.

众所周知，手性烛石因其精致的三维大环框架而具有多种功能。然而，这些化合物的催化不对称合成在很大程度上仍未得到探索，并构成了一项重大挑战。在此，我们报告了一种前所未有的手性钙[4]炔的对映选择性电化学合成方法。我们的方法基于 3d 金属钴催化的原手性大环框架的不对称 C-H 乙酰氧基化。我们使用了易于获得和修饰的手性水杨酰噁唑啉（Salox）作为配体，以有效调节对映体选择性。该方法在电化学温和的条件下顺利进行，并与多种羧酸兼容，包括芳基羧酸和三级、二级、一级脂肪族羧酸，得到了多种酰氧基化的钙[4]炔，收率高（达 94%），对映体选择性好（95-99% ee）。该方法的合成实用性通过放大反应和固有手性大环产物的衍生化得到了证明。

引用次数: 0

Highly efficient synthesis of lysergic acid using engineered budding yeast† 利用工程芽殖酵母高效合成麦角酸

IF 9.3 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2024-09-30 DOI: 10.1039/d4gc03756a

Lysergic acid (LA) is the basic precursor for the biosynthesis of various ergot alkaloids of pharmaceutical importance. The heterologous biosynthesis of LA in microbes is a promising method to reduce industrial dependence on highly costly and toxic crop-pathogenic ergot fungi. However, the biosynthetic efficiency of LA remains unsatisfactory because of the lack of effective pathways and low heterologous production performance. In this work, a microbial host, specifically a Saccharomyces cerevisiae strain, was constructed by applying a metabolic engineering strategy for efficient LA production. The SCH9 knockout was identified as a key factor for enhancing LA yield. Transcriptional analysis revealed that SCH9 deletion significantly enhanced peroxisomal metabolism and cellular translation. Accordingly, tailored approaches were designed to optimize the activities of two rate-limiting enzymes, EasC and CloA, in SCH9 deletion strains. The relocation of EasC to peroxisomes combined with PEX34 overexpression clearly increased the catalytic activity of these enzymes, increasing LA production by 2.31-fold. Moreover, spatial reorientation of the cytochrome P450 CloA and its reductase on the endoplasmic reticulum was performed, which improved electron transfer efficiency, resulting in a 36.8% improvement in LA production. These engineering strategies finally led to a 17.4-fold increase in the LA titre. The final engineered strain produced 509.8 mg L⁻¹ LA under 50 L fed-batch fermentation, yielding the highest reported titre for heterologous hosts. These findings demonstrated a green alternative to the current ergot-based routes, offering a versatile platform for the sustainable, large-scale fermentation of pharmaceutical ergot alkaloids.

麦角酸（LA）是生物合成各种具有重要药用价值的麦角生物碱的基本前体。在微生物中异源生物合成 LA 是一种很有前途的方法，可以减少工业对高成本、高毒性的作物致病麦角菌的依赖。然而，由于缺乏有效途径和异源生产性能低下，LA 的生物合成效率仍不令人满意。在这项工作中，通过应用高效生产 LA 的代谢工程策略，构建了微生物宿主，特别是酿酒酵母菌株。SCH9基因敲除被认为是提高LA产量的关键因素。转录分析表明，SCH9 基因缺失可显著增强过氧物酶体代谢和细胞翻译。因此，设计了量身定制的方法来优化 SCH9 基因缺失菌株中两种限速酶 EasC 和 CloA 的活性。将 EasC 移至过氧化物酶体并结合 PEX34 的过表达，明显提高了这两种酶的催化活性，使 LA 的产量增加了 2.31 倍。此外，还对内质网上的细胞色素 P450 CloA 及其还原酶进行了空间定向，提高了电子传递效率，从而使 LA 产量提高了 36.8%。这些工程策略最终使 LA 滴度提高了 17.4 倍。最终的工程菌株在 50 升饲料批量发酵条件下产生了 509.8 mg L-1 的 LA，是目前报道的异源宿主最高滴度。这些研究结果表明，目前基于麦角的发酵路线是一种绿色替代方案，为可持续、大规模发酵药用麦角生物碱提供了一个多功能平台。

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引用次数: 0

Molecular structural engineering of donor–acceptor-based porous organic polymers for sulfide photooxidation in water: a sustainable approach† 用于水中硫化物光氧化的供体-受体型多孔有机聚合物的分子结构工程：一种可持续的方法

IF 9.3 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2024-09-30 DOI: 10.1039/d4gc03255a

The utilization of mild and environment-friendly reaction conditions for the photocatalytic oxidation of sulfides to highly valuable sulfoxides represents a sustainable approach that is highly desirable yet quite challenging. Herein, we present a novel approach to enhance the photocatalytic oxidation of sulfides in water by molecular structural engineering of donor–acceptor (D–A) based polymeric networks. By incorporating electron-deficient heptazine or triazine units as acceptors and electron-rich 2,5-diamino fluorene as donors, a synergistic effect is achieved, promoting efficient charge separation upon light absorption. The two polymeric networks namely HEP-FL and TZ-FL efficiently carried out selective oxidation of sulfides to sulfoxide with 100% conversion within 1.3 h and 3.5 h, respectively under blue light irradiation. Through advanced spectroscopic and electrochemical measurements, the correlation between molecular structures and optoelectronic properties is elucidated, unveiling tunable band structures and exciton binding energies. Notably, the heptazine-containing polymeric network (HEP-FL) exhibited superior charge separation efficiency and enhanced catalytic activity, attributed to improved electron delocalization and reduced exciton binding energy. Additionally, we have performed green metrics calculations for the synthesis of sulfoxide using HEP-FL as a photocatalyst to prove the sustainability of the reaction system. These findings underscore the significant prospects of donor–acceptor-based polymeric networks as highly effective photocatalysts for selective oxidation reactions, highlighting their potential to advance environmentally conscious practices in organic synthesis and industrial applications.

利用温和、环境友好的反应条件将硫化物光催化氧化成高价值的硫氧化物是一种可持续的方法，这种方法非常可取，但也相当具有挑战性。在此，我们提出了一种新方法，通过基于供体-受体（D-A）聚合物网络的分子结构工程来增强硫化物在水中的光催化氧化。通过加入缺电子的庚嗪或三嗪单元作为受体，富电子的 2,5 二甲基芴作为供体，实现了协同效应，促进了光吸收时电荷的有效分离。在蓝光照射下，HEP-FL 和 TZ-FL 两种聚合物网络分别在 1.3 小时和 3.5 小时内高效地将硫化物选择性氧化为亚砜，转化率达到 100%。通过先进的光谱和电化学测量，阐明了分子结构与光电特性之间的相关性，揭示了可调带状结构和激子结合能。值得注意的是，含有庚嗪的聚合物网络（HEP-FL）表现出卓越的电荷分离效率和更强的催化活性，这归因于电子析出的改善和激子结合能的降低。此外，我们还利用 HEP-FL 作为光催化剂，对氧化亚砜的合成进行了绿色指标计算，以证明反应系统的可持续性。这些发现强调了以供体-受体为基础的聚合物网络作为选择性氧化反应的高效光催化剂的重要前景，凸显了它们在有机合成和工业应用中推进环保意识的潜力。

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引用次数: 0

Recent catalytic innovations in furfural transformation 最近在糠醛转化方面的催化创新

IF 9.3 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2024-09-30 DOI: 10.1039/d4gc01983k

To address the problem of non-renewable resources and energy shortages, converting biomass, the only renewable carbon resource on Earth, into various fine chemicals holds significant value. Furfural stands out as one of the most promising platform compounds derived from lignocellulosic biomass. Due to its highly functional molecular structure, furfural can be selectively converted into various fuels and high-value compounds. This review discusses recent developments in furfural production and its conversion into related chemicals, such as furfuryl alcohol, γ-valerolactone, pentanediols, and nitrogen-containing compounds. It provides an in-depth understanding of the catalysts, systems, and mechanisms used in the selective transformation of furfural. The review also explores primary pathways and catalytic mechanisms, with a focus on advances in heterogeneous catalytic systems. Furthermore, it outlines future research directions and offers insights into potential applications in this field. This review presents several research trends, aiming to provide innovative ideas for further exploration of furfural downstream products in a greener, more efficient, and cost-effective manner.

为解决不可再生资源和能源短缺问题，将生物质这一地球上唯一的可再生碳资源转化为各种精细化学品具有重要价值。糠醛是从木质纤维素生物质中提取的最有前途的平台化合物之一。由于糠醛具有高功能性分子结构，因此可选择性地转化为各种燃料和高价值化合物。本综述讨论了糠醛生产及其转化为相关化学品（如糠醇、γ-戊内酯、戊二醇和含氮化合物）的最新进展。报告深入介绍了用于糠醛选择性转化的催化剂、系统和机制。该综述还探讨了主要途径和催化机制，重点关注异质催化系统的进展。此外，它还概述了未来的研究方向，并对这一领域的潜在应用提出了见解。本综述介绍了几种研究趋势，旨在为以更环保、更高效、更具成本效益的方式进一步探索糠醛下游产品提供创新思路。

引用次数: 0

Environmentally friendly Miyaura Borylations allowing for green, 1-pot borylation/Suzuki–Miyaura couplings† 环保型 Miyaura 硼酰化技术可实现绿色、1-锅硼酰化/铃木-Miyaura 偶联反应

IF 9.3 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2024-09-30 DOI: 10.1039/d4gc03115f

Current routes to boronic acids and their corresponding esters to be used in subsequent Suzuki–Miyaura (SM) cross couplings impact the cost, waste, and safety concerns associated with generating these materials. A new method for installing the ethyl pinacol boronic ester, or B(Epin) derivative leads to stable borylated products under near-neat conditions using high concentrations of a green solvent and moderate reaction temperatures, catalyzed by relatively low palladium loadings. Alternatively, the newly fashioned Ar–B(Epin) can be generated in situ and used directly in the same pot for SM reactions leading to aromatic and heteroaromatic residues characteristic of the biaryl products being formed. An array of complex targets, including API-related products, can be generated via this green and environmentally responsible methodology.

目前用于后续铃木-宫浦（SM）交叉偶联反应的硼酸及其相应酯类的制备路线会影响到与生成这些材料相关的成本、废物和安全问题。一种安装频哪醇乙硼酸酯或 B(Epin)衍生物的新方法，在相对较低的钯载量催化下，使用高浓度的绿色溶剂和适中的反应温度，在近乎无水的条件下生成稳定的硼酰化产物。另外，还可以在原位生成新的 Ar-B（表嘌呤），并直接在同一锅中用于 SM 反应，从而产生具有双芳基产物特征的芳香族和杂芳香族残留物。通过这种绿色环保的方法，可以生成一系列复杂的目标物，包括原料药相关产品。

引用次数: 0

Insight into aqueous electrolyte additives: unraveling functional principles, electrochemical performance, and beyond† 深入了解水性电解质添加剂：揭示功能原理、电化学性能及其他方面的问题

IF 9.3 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2024-09-30 DOI: 10.1039/d4gc02619e

Aqueous electrolyte additives are considered one of the most promising agents for improving the cycling stability and practicality of aqueous zinc-ion batteries (AZIBs) due to their multiple functions, low cost, and easy operation. The application of these electrolyte additives could significantly suppress the corrosion reaction, dendrite growth, and the hydrogen evolution reaction originating from the zinc anodes. In light of the intensive research of electrolyte additives and the significant progress that have been made in recent years, this review will focus on the mechanism and nature behind the improved performance contributed by the additives. A comprehensive overview of the origins of the challenges above will be presented firstly. Furthermore, the basic function principles of most reported additives are summarized and categorized, aiming to induce a deep and logical consideration of the use of the electrolyte additives in practical or large capacity cells. Finally, this review outlines the prospective advancement of electrolyte additives, inspiring the application of advanced characterization techniques in enhancing the understanding of AZIBs and laying the groundwork for the possibility of commercialization of AZIBs.

水性电解质添加剂具有功能多、成本低、操作简便等特点，被认为是提高锌离子水性电池（AZIB）循环稳定性和实用性的最有前途的添加剂之一。这些电解质添加剂的应用可以显著抑制锌阳极的腐蚀反应、枝晶生长和氢进化反应。鉴于近年来对电解质添加剂的深入研究和取得的重大进展，本综述将重点探讨添加剂改善性能背后的机理和本质。首先，将全面概述上述挑战的起源。此外，还将对大多数已报道的添加剂的基本功能原理进行总结和分类，旨在引导人们对电解质添加剂在实用或大容量电池中的使用进行深入而合理的思考。最后，本综述概述了电解质添加剂的发展前景，激励人们应用先进的表征技术加深对 AZIBs 的了解，并为 AZIBs 商业化的可能性奠定基础。

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引用次数: 0

Solvent-free Markovnikov hydroamination of vinylarenes with carboxamides: a heterogeneous catalytic approach using Hβ zeolite† 乙烯基烯烃与羧酰胺的无溶剂马尔可夫尼科夫氢化反应：使用 Hβ 沸石的异相催化方法

IF 9.3 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2024-09-30 DOI: 10.1039/d4gc04264f

The synthesis of carbon–heteroatom bonds, a crucial element in organic chemistry, often requires obstacles in direct amine integration with olefins. This study introduces a sustainable approach for producing nitrogen-bearing molecules through the Markovnikov hydroamination of vinylarenes with carboxamides, employing Hβ zeolite as an effective heterogeneous catalyst in a solvent-free environment. We explored the method's adaptability over various substrates, achieving consistently high yields and regioselectivity in the resultant products. The procedure's scalability to gram-level production and the catalyst's sustainable reuse for multiple cycles (up to five) underscores its viability for industrial application, indicating a significant increase in organic synthesis activity.

碳-杂原子键是有机化学中的一个重要元素，其合成通常需要直接胺与烯烃的结合。本研究介绍了一种通过乙烯基醚与羧酰胺的马尔可夫尼科夫氢化反应生产含氮分子的可持续方法，采用 Hβ 沸石作为无溶剂环境中的有效异相催化剂。我们探索了该方法对各种基质的适应性，结果产品始终保持高产率和区域选择性。该方法可扩展到克级生产，催化剂可持续重复使用多个周期（最多五个周期），这凸显了其工业应用的可行性，表明有机合成活性显著提高。

引用次数: 0

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