Advanced Synthesis & Catalysis最新文献

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Multifunctionalization of N‐Heterocyclic Carbene Boranes by a Single Metal‐free Photocatalyst 单金属光催化剂催化N -杂环碳硼烷的多功能化

IF 5.4 2区化学 Q2 CHEMISTRY, APPLIED

Advanced Synthesis & Catalysis

Pub Date : 2025-01-08 DOI: 10.1002/adsc.202401440

Feng-Xing Li, Yu Liu, Ke Zhang, Cheng Wang, Ji-Xin Yu, Xiao-Jun He, Ge Liang, Hong-Yu Hou, Chen-Ho Tung, Li-Zhu Wu

Selective access to densely functionalized boranes, with identical or distinct functional groups at the boron center, has great potentials in materials science, organic synthesis and drug discovery. However, assembling multifunctional boranes was heavily dependent on hydrogen‐atom‐transfer (HAT) at high temperatures, hazardous radical initiators, metal photocatalysts and HAT reagents, respectively. Simultaneously, competitive side reactions such as polymerizations and regioisomers formation remain highly challenging. Herein, a programmable multifunctionalization of N‐heterocyclic carbene (NHC) boranes is developed for the first time powered by a single, metal‐free photocatalyst, in which boryl radicals from sequential substituted boranes are generated instead of polymerizations. This robust and versatile catalytic system leads to an extremely broad variety of boranes incorporated with diverse alkyl or alkenyl groups in high chemo‐ and regioselectivities.

选择性获得在硼中心具有相同或不同官能团的密集功能化硼烷，在材料科学、有机合成和药物发现方面具有巨大的潜力。然而，组装多功能硼烷主要依赖于高温下的氢原子转移（HAT）、危险自由基引发剂、金属光催化剂和HAT试剂。同时，竞争性副反应，如聚合和区域异构体的形成仍然是高度挑战性的。本文首次开发了N -杂环碳（NHC）硼烷的可编程多功能化，该多功能化由单一的无金属光催化剂驱动，其中顺序取代的硼烷产生硼基自由基，而不是聚合。这种强大的和通用的催化系统导致极广泛的种类硼烷结合不同的烷基或烯基在高化学和区域选择性。

引用次数: 0

Phosphorus Fluoride Exchange (PFEx) Click Chemistry: 2‐Substituted‐alkynyl‐1‐cyclotriphosphazene (SACP) Hubs for Diversity Oriented Clicking 氟化磷交换（PFEx）点击化学：2‐取代-炔基- 1‐环三磷腈（SACP）枢纽，用于多样性导向点击

IF 5.4 2区化学 Q2 CHEMISTRY, APPLIED

Advanced Synthesis & Catalysis

Pub Date : 2025-01-08 DOI: 10.1002/adsc.202401573

Zifei Wang, Dharmendra S. Vishwakarma, Shoujun Sun, Qiyao Huang, Soumyaranjan Pati, Robert M. Johnson, Michael R. Rufrano, Milan Gembicky, Joshua Homer, John Edward Moses

Phosphorus Fluoride Exchange (PFEx) is a new click chemistry technology that hinges on the creation of innovative hubs to unlock its potential and broaden its applications. In this study, we outline some guiding principles for PFEx hub development and validate these principles by developing a new hub, 2‐substituted‐alkynyl‐1‐cyclotriphosphazenes (SACPs). These SACPs serve as versatile PFEx hubs with stable functionality and orthogonal reactivity, exemplifying their utility within the Diversity Oriented Clicking (DOC) framework. We demonstrate that SACPs interact with various 1,3‐dipoles, enabling the synthesis of phosphorus‐rich compounds through sequential cycloaddition and PFEx reactions, thus pioneering new synthetic routes for wide application of click chemistry.

氟化磷交换（PFEx）是一种新的点击化学技术，它依赖于创建创新中心来释放其潜力并扩大其应用范围。在本研究中，我们概述了PFEx集线器开发的一些指导原则，并通过开发一种新的集线器，2 -取代-炔基- 1 -环三磷腈（SACPs）来验证这些原则。这些sacp作为多功能PFEx集线器，具有稳定的功能和正交反应性，例证了它们在多样性定向点击（DOC）框架中的实用性。我们证明了SACPs与各种1,3偶极子相互作用，使富磷化合物能够通过顺序环加成和PFEx反应合成，从而开辟了新的合成路线，广泛应用于点击化学。

引用次数: 0

Mechanochemical Pd-Catalyzed Cross-Coupling of In-Situ Generated Reformatsky Zn-Enolates pd催化原位生成Reformatsky锌烯醇酯的机械化学交叉偶联

IF 5.4 2区化学 Q2 CHEMISTRY, APPLIED

Advanced Synthesis & Catalysis

Pub Date : 2025-01-07 DOI: 10.1002/adsc.202401403

Tomáš Čarný, Dominika Mravcová, Barbora Steinhüblová, Radovan Šebesta

Transition-metal-catalyzed α-arylations of carbonyl compounds have shown to be a useful strategy for the late-stage synthesis of α-arylesters. However, the use of strong basic conditions and difficult handling necessary for the in-situ preparation of enolates is a major disadvantage. On the other hand, using Reformatsky zinc-enolates can overcome these challenges. Moreover, mechanochemical in-situ activation of zinc is even more beneficial. Herein, we report mechanochemical Pd-catalyzed cross-coupling between in-situ generated Reformatsky Zn-enolates and aryl halides. This operationally simple procedure affords α-arylated esters or amides using an affordable catalytic system. Reactions were carried under air and ambient conditions using granulated zinc without the need for its pre-activation. Less reactive and commercially more affordable aryl bromides afforded the desired products in good to excellent yields in comparison to aryl iodides. The optimized conditions were applied in scale-up reaction and in the synthesis of α-arylated esters, amides, and derivatives of natural products.

过渡金属催化羰基化合物的α-芳基化已被证明是α-芳基化合物合成后期的一种有用的策略。然而，原位制备烯醇酯所需的强基础条件和困难的处理是一个主要缺点。另一方面，使用Reformatsky锌烯醇化物可以克服这些挑战。此外，锌的机械化学原位活化更有益。在此，我们报道了原位生成的Reformatsky锌烯醇化物和芳基卤化物之间的机械化学pd催化交叉偶联。这个操作简单的程序提供α-芳基化酯或酰胺使用负担得起的催化系统。反应是在空气和环境条件下进行的，使用粒状锌，不需要它的预活化。与芳基碘化物相比，芳基溴的反应性较低，商业上更实惠，可提供所需产品的良好至优异收率。将优化后的条件应用于放大反应和天然产物α-芳基化酯、酰胺及其衍生物的合成。

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引用次数: 0

Structure‐guided engineering of oleate hydrates for the synthesis of small chiral alcohols without decoy molecule 无诱骗分子油酸水合物合成小手性醇的结构导向工程

IF 5.4 2区化学 Q2 CHEMISTRY, APPLIED

Advanced Synthesis & Catalysis

Pub Date : 2025-01-07 DOI: 10.1002/adsc.202401358

Bernhard Hauer, Natalie Haerterich, Andreas Schneider, Philip Horz, Nicolas D. Travnicek

Small and chiral secondary alcohols are sought‐after compounds that are frequently used in the synthesis of biologically active compounds. However, their stereochemically correct synthesis remains a challenge for the chemical industry. Synthetic routes are restrained by multiple steps and thus low atom efficiency. Here we employ engineered variants from the oleate hydratase from E. meningoseptica to produce chiral C5‐C10 secondary alcohols within a single step. First, we established a two‐phase system (2‐PS) to trap the volatile substrates/products which facilitated semi‐rational mutagensis in the active site and tunnel of the enzyme. These efforts led to variants with an up to 20‐fold increase in catalytic activity and >99% ee, notably, without the use of a decoy molecule. Computational analysis indicated structural changes in the tunnel radius, ligand transport and energy profiles, which gave us hints to explain the enhanced performance of the variants. Interestingly, scaling up the reaction volume demonstrated significant increases in product concentrations, leading up to a 100‐fold increase in comparison to the current benchmark. This new 2‐PS and the engineered enzyme variants offer a promising approach for a scalable, asymmetric hydration of small unactivated alkenes, which would drastically ease the access to chiral alcohol‐based pheromones or drugs.

小的和手性仲醇是一种广受追捧的化合物，经常用于合成生物活性化合物。然而，它们的立体化学正确合成仍然是化学工业的一个挑战。合成路线受到多个步骤的限制，因而原子效率较低。在这里，我们使用来自脑膜炎脓毒杆菌的油酸水合酶的工程变体，在一个步骤内产生手性C5‐C10仲醇。首先，我们建立了一个两相系统（2‐PS）来捕获易挥发的底物/产物，这些底物/产物促进了酶活性位点和通道的半理性诱变。这些努力使变体的催化活性提高了20倍，ee提高了99%，特别是在没有使用诱饵分子的情况下。计算分析显示了隧道半径、配体输运和能量分布的结构变化，这为解释变体的性能增强提供了线索。有趣的是，扩大反应体积表明产物浓度显著增加，与当前基准相比增加了100倍。这种新的2 - PS和工程酶变体为小型非活化烯烃的可扩展、不对称水合提供了一种有前途的方法，这将大大简化手性醇基信息素或药物的获取。

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引用次数: 0

Front Cover Picture: Asymmetric [3+3] Cycloaddition of N-Vinyl Oxindole Nitrones with 2-Indolylmethanols to Prepare Spirooxindole[1,2]oxazines (Adv. Synth. Catal. 24/2024) 封面图：n -乙烯基氧吲哚硝基酮与2-吲哚甲醇的不对称[3+3]环加成制螺旋氧吲哚[1,2]恶嗪（ad . Synth.）Catal。24/2024)

IF 5.4 2区化学 Q2 CHEMISTRY, APPLIED

Advanced Synthesis & Catalysis

Pub Date : 2024-12-30 DOI: 10.1002/adsc.202401504

Ning Zou, Yu-Zheng Wu, Xin-Yi Zhong, Cui Wei, Li-Min Liao, Dong-Liang Mo, Wen-Jun Zhou

The front cover illustrates a chiral phosphoric acid (CPA) catalyzed enantioselective [3+3] cycloaddition of N-vinyl oxindole nitrones and 2-indolylmethanols, which was utilized to prepare a variety of spirooxindole[1,2]oxazines. Details can be found in Communication by Wen-Jun Zhou, and co-workers (N. Zou, Y.-Z. Wu, X.-Y. Zhong, C. Wei, L.-M. Liao, D.-L. Mo, W.-J Zhou, Adv. Synth. Catal. 2024, 366, 4962-4967; DOI: 10.1002/adsc.202400533))

上图为手性磷酸（CPA）催化的n -乙烯基氧吲哚硝基和2-吲哚甲醇对映选择性[3+3]环加成反应，制备了多种螺肟吲哚[1,2]恶嗪。详细内容可参见周文君和同事（邹宁，y.z。）吴,X.-Y。钟，魏翀，李明明。廖,D.-L。莫，周炜杰，广告合成。中文信息学报。2024,366,4962-4967；DOI: 10.1002 / adsc.202400533))

引用次数: 0

CORRIGENDUM: 1-Oxa-2,6-Diazaspiro[3.3]-heptane as a New Potential Piperazine Bioisostere – Flow-Assisted Preparation and Derivatisation by Strain-Release of Azabicyclo[1.1.0]butanes 勘误：1- oxa -2,6-重氮杂环[3.3]-庚烷作为一种新的潜在哌嗪类生物异构体-氮杂环[1.1.0]丁烷的流动辅助制备和衍生化

IF 5.4 2区化学 Q2 CHEMISTRY, APPLIED

Advanced Synthesis & Catalysis

Pub Date : 2024-12-30 DOI: 10.1002/adsc.202401389

In the research article by Elena Graziano, Philipp Natho, Michael Andresini, Fabrizio Mastrolorito, Iktedar Mahdi, Ernesto Mesto, Marco Colella, Leonardo Degennaro, Orazio Nicolotti, and Renzo Luisi, in Issue 18, 2024, pp. 3894–3902 (DOI: 10.1002/adsc.202400781), the acknowledgement section should have included mention of additional financial support. R.L., L.D., M.A. acknowledge financial support from the European Commission – Horizon Europe Framework, project SusPharma grant agreement No 101057430. I.M. acknowledges funding from the European Commission′s Horizon Europe research and innovation programme through the Marie Skłodowska-Curie doctoral network “GreenDigiPharma” (grant agreement No 101073089). The authors apologize for this oversight

在Elena Graziano， Philipp Natho, Michael Andresini, Fabrizio Mastrolorito, Iktedar Mahdi, Ernesto Mesto, Marco Colella, Leonardo Degennaro， Orazio Nicolotti和Renzo Luisi的研究文章中，在第18期，2024，第3894-3902页（DOI: 10.1002/ adc .202400781），致谢部分应该包括提到额外的财政支持。r.l.， L.D， M.A.承认欧盟委员会-地平线欧洲框架的财政支持，项目SusPharma资助协议号101057430。imm通过Marie Skłodowska-Curie博士网络“GreenDigiPharma”（资助协议号101073089）承认欧盟委员会的“地平线欧洲”研究和创新计划的资助。作者为这个疏忽道歉

引用次数: 0

Halogen-Atom Engineering on Aromatic-Core in Tethered Small Molecule Acceptors for High-Performance Polymer Solar Cells 高性能聚合物太阳能电池系链小分子受体芳香族核卤素原子工程

IF 5.4 2区化学 Q2 CHEMISTRY, APPLIED

Advanced Synthesis & Catalysis

Pub Date : 2024-12-29 DOI: 10.1002/smll.202411409

Shanshan Jian, Yu Zang, Shixin Meng, Ming Zhang, Zhengkai Li, Qi Chen, Hongru Chen, Qingyuan Wang, Shanshan Chen, Lingwei Xue, Xiuyu Wang, Zhi-Guo Zhang

Tethered small molecular acceptors (SMAs), where multiple SMA-subunits are connected to the aromatic core via flexible chains, are proposed to suppress thermodynamic relaxation when blended with polymer donors to construct stable polymer solar cells (PSCs). However, optimizing their chemical structure to further enhance device performance remains a challenge, requiring careful fine-tuning between molecular aggregation and photovoltaic efficiency. In this study, the photovoltaic properties of tethered dimers are effectively modulated simply through halogen-atom engineering on the aromatic core. Specifically, DY-Cl with a chlorine atom and DY-Br with a bromine atom are designed. The study revealed the chloride acceptor enhances the intermolecular interaction, promotes charge transport, and optimizes the morphology of the active layer compared with its bromide counterpart. Notably, DY-Cl based PSCs achieves a power conversion efficiency of 18.72%, maintaining over 80% of initial PCE after operating for 1000 h. These findings underscore the potential advantages of halogen-atom engineering on tethered acceptors as a straightforward yet effective method to achieve high efficiency and stable PSCs.

拴系小分子受体（SMAs），其中多个sma亚基通过柔性链连接到芳核，提出抑制热力学松弛时，与聚合物供体混合，以构建稳定的聚合物太阳能电池（PSCs）。然而，优化它们的化学结构以进一步提高器件性能仍然是一个挑战，需要在分子聚集和光伏效率之间进行仔细的微调。在本研究中，系链二聚体的光伏性质可以通过在芳香核上的卤素原子工程来有效地调制。具体来说，设计了含氯原子的镝- cl和含溴原子的镝- br。研究发现，与溴离子受体相比，氯离子受体增强了分子间相互作用，促进了电荷传输，并优化了活性层的形态。值得注意的是，基于DY-Cl的PSCs的功率转换效率达到18.72%，在运行1000小时后保持超过初始PCE的80%。这些发现强调了系系受体上卤素原子工程作为一种简单而有效的方法获得高效率和稳定的PSCs的潜在优势。

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引用次数: 0

Efficient Cu-catalyzed Asymmetric Alkylation and Application in the Total Synthesis of Phallotoxins and Virotoxins 高效铜催化不对称烷基化及其在赘生物毒素和病毒毒素全合成中的应用

IF 5.4 2区化学 Q2 CHEMISTRY, APPLIED

Advanced Synthesis & Catalysis

Pub Date : 2024-12-26 DOI: 10.1002/adsc.202401338

Guodu Liu, Lin Fan, Jiashan Li, Xinlong Yan, Zongwei Li, Yang Wang, Le Pan

Asymmetric alkylation is one of the most important methods for synthesis of chiral unnatural α-substituted α-amino acids. Herein, we reported the asymmetric alkylation catalyzed by Cu/(4S,2R)-tBu-Phosferrox catalyst. This catalyst exhibits the highest catalytic performance in the asymmetric alkylation at catalyst loading as low as 1.0 mol %, giving the desired products with up to 95% yield and >99% ee, which is the best results to date. Furthermore, this method was successfully applied to the scalable practical synthesize of unnatural amino acid 4,5-OH-Leu, which could be directly used in the total syntheses of phalloidin, phallacidin, other four phallotoxins and six virotoxins.

不对称烷基化反应是合成手性非天然α-取代α-氨基酸的重要方法之一。本文报道了Cu/(4S,2R)-tBu-Phosferrox催化剂催化的不对称烷基化反应。在负载低至1.0 mol %时，该催化剂在不对称烷基化反应中表现出最高的催化性能，产率高达95%，ee达99%，这是迄今为止最好的结果。此外，该方法还成功应用于非天然氨基酸4,5- oh - leu的规模化实际合成，可直接用于阴茎素、阴茎酸素等4种阴茎素毒素和6种病毒毒素的全合成。

引用次数: 0

Regiodivergent Reactions of 2-Alkynl Aziridines with Grignard Reagents 2-炔基叠氮嘧啶与格氏试剂的区域发散反应

IF 5.4 2区化学 Q2 CHEMISTRY, APPLIED

Advanced Synthesis & Catalysis

Pub Date : 2024-12-23 DOI: 10.1002/adsc.202401311

Wen-Tao Ji, A-Nan Ping, Gaosheng Yang, Zhuo Chai

Herein, we report regiodivergent nucleophilic attack of Grignard reagents to 2-alkynyl aziridines. Under the catalysis of a Cu(I)-diphosphine complex, benzylic Grignard reagents add to the carbon-carbon triple bond of the aziridines to deliver α-allenylamines in moderate to excellent yields; the direct addition of the Grignard reagents to the aziridines in the absence of catalyst provided homopropargylic amine derivatives. Both reactions could proceed in highly enantiospecific ways. Further synthetic manipulations of these products enable rapid access to diverse useful heterocyclic molecular scaffolds.

本文报道了格氏试剂对2-炔基偶氮嘧啶的区域发散性亲核攻击。在Cu(I)-二膦配合物的催化下，苯基格氏试剂加入到氮嘧啶的碳-碳三键上，以中等至优异的收率传递α-烯胺；在没有催化剂的情况下，将格氏试剂直接加成到叠氮胺上，得到了同丙基胺衍生物。这两种反应都可能以高度对映特异性的方式进行。这些产物的进一步合成操作可以快速获得各种有用的杂环分子支架。

引用次数: 0

Three‐ and Seven‐membered Annulenones as a Lewis Base Catalyst for Enantioselective meso‐Epoxide Opening 三元和七元环烯酮作为路易斯碱催化剂对映选择性中环氧化合物打开

IF 5.4 2区化学 Q2 CHEMISTRY, APPLIED

Advanced Synthesis & Catalysis

Pub Date : 2024-12-23 DOI: 10.1002/adsc.202401186

Sachie Arae, Yasushi Shimoda, Mizuki Kuwajima, Shunsuke Kotani, Makoto Nakajima

This is the report on the Lewis base catalysis of annulenones. Additionally, the synthesis of chiral annulenone catalysts and their application in asymmetric ring‐opening reactions of meso‐epoxides is shown. Annulenones, such as cyclopropenones and tropones, function as Lewis bases owing to their inherent polarity caused by aromaticity, resulting in the activation of silicon tetrachloride, which catalyzes the ring‐opening reaction of meso‐epoxides. Moreover, various chiral annulenone catalysts have been designed and synthesized, and microwave irradiation has been shown to improve the synthetic efficiency of chiral tropones. The chiral annulenones successfully catalyzed the asymmetric ring‐opening reaction of meso‐epoxides, resulting in the formation of 1,2‐chlorohydrins in a high yield and high enantioselectivity (up to 90% ee in 96% yield). These results represent the example of three‐ and seven‐membered annulenones as a chiral Lewis base catalyst.

这是关于环烯酮的路易斯碱催化作用的报告。此外，还介绍了手性环烯酮催化剂的合成及其在中介环氧化物不对称开环反应中的应用。环烯酮，如环丙烯酮和tropones，由于其固有的由芳香性引起的极性而发挥路易斯碱的作用，导致四氯化硅的活化，从而催化中介环氧化物的开环反应。此外，还设计和合成了多种手性环烯酮催化剂，并证明微波辐射可以提高手性环酮的合成效率。手性环烯酮成功地催化了中环氧化物的不对称开环反应，生成了高产率和高对映选择性的1,2 -氯丙烷（96%产率，高达90% ee）。这些结果代表了三元和七元环烯酮作为手性路易斯碱催化剂的例子。

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全部化学•材料生命科学医学物理工程技术环境•农林材料科学地球科学法学管理学化学环境科学与生态学计算机科学教育学经济学农林科学人文科学生物学数学物理与天体物理心理学综合性期刊其他工业工程理学历史学农学文学信息工程

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