Organic chemistry frontiers : an international journal of organic chemistry最新文献

英文中文

Light-promoted cobalt-catalyzed radical Markovnikov hydrothiolation of alkenes with N-arylsulfenyl phthalimides 光促进钴催化烯烃与n -芳基亚砜基邻苯二胺的自由基Markovnikov氢硫化反应

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-08-13 Epub Date: 2025-08-22 DOI: 10.1039/d5qo01020a

Xiang-Rui Li , Rong-Jin Zhang , Ting-Ting Miao , Yonghong Xiao , Kun-Quan Chen , Jian-Ji Zhong

In recent years, transition-metal hydride catalysis has emerged as a powerful strategy for radical Markovnikov hydrothiolation of alkenes, providing efficient access to branched thioethers. However, this approach remains underexplored, with existing methods often hampered by limitations such as the reliance on silane reductants, the need for specialized sulfide nucleophiles or radical acceptors, or the use of external oxidants. Herein, we report a new light-promoted cobalt-catalyzed system that employs Hantzsch ester as a mild hydride source for the radical Markovnikov hydrothiolation of alkenes using N-arylsulfenyl phthalimides as thiyl radical precursors. Notably, when allylic arenes were employed as substrates, a metal-hydride hydrogen atom transfer (MHAT)/retro-MHAT process occurred, enabling the synthesis of branched benzyl sulfides, which was unattainable under conventional catalytic conditions. Mechanistic investigations support the proposed reaction pathway. This method exhibits excellent regioselectivity, broad functional group compatibility, and applicability in late-stage functionalization.

近年来，过渡金属氢化物催化已成为烯烃自由基马尔可夫尼科夫氢硫化的有力策略，提供了分支硫醚的有效途径。然而，这种方法仍然没有得到充分的探索，现有的方法经常受到诸如依赖硅烷还原剂，需要专门的硫化物亲核试剂或自由基受体，或使用外部氧化剂等限制的阻碍。本文报道了一种新的光促进钴催化体系，该体系采用汉氏酯作为温和氢化物源，以n -芳基亚砜基酞酰亚胺作为噻基自由基前体，用于烯烃的Markovnikov氢硫化。值得注意的是，当烯丙芳烃作为底物时，发生了金属氢化物氢原子转移(MHAT)/反MHAT过程，可以合成支化苄基硫化物，这在常规催化条件下是无法实现的。机理研究支持所提出的反应途径。该方法具有良好的区域选择性、广泛的官能团相容性和后期功能化的适用性。

{"title":"Light-promoted cobalt-catalyzed radical Markovnikov hydrothiolation of alkenes with N-arylsulfenyl phthalimides","authors":"Xiang-Rui Li , Rong-Jin Zhang , Ting-Ting Miao , Yonghong Xiao , Kun-Quan Chen , Jian-Ji Zhong","doi":"10.1039/d5qo01020a","DOIUrl":"10.1039/d5qo01020a","url":null,"abstract":"<div><div>In recent years, transition-metal hydride catalysis has emerged as a powerful strategy for radical Markovnikov hydrothiolation of alkenes, providing efficient access to branched thioethers. However, this approach remains underexplored, with existing methods often hampered by limitations such as the reliance on silane reductants, the need for specialized sulfide nucleophiles or radical acceptors, or the use of external oxidants. Herein, we report a new light-promoted cobalt-catalyzed system that employs Hantzsch ester as a mild hydride source for the radical Markovnikov hydrothiolation of alkenes using <em>N</em>-arylsulfenyl phthalimides as thiyl radical precursors. Notably, when allylic arenes were employed as substrates, a metal-hydride hydrogen atom transfer (MHAT)/<em>retro</em>-MHAT process occurred, enabling the synthesis of branched benzyl sulfides, which was unattainable under conventional catalytic conditions. Mechanistic investigations support the proposed reaction pathway. This method exhibits excellent regioselectivity, broad functional group compatibility, and applicability in late-stage functionalization.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 23","pages":"Pages 6548-6555"},"PeriodicalIF":0.0,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144898832","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}

引用次数: 0

Rhodium-catalyzed hydroselenation of unsymmetric 1,3-dienes with 3,4-Markovnikov regioselectivity 铑催化具有3,4- markovnikov区选择性的不对称1,3-二烯的加氢硒化反应

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-08-13 Epub Date: 2025-08-14 DOI: 10.1039/d5qo00926j

Anee Taj , Chen Cui , Zhenwei Shi , Xuebin Huang , Xiao-Hui Yang

Catalytic hydroselenation of alkenes represents one of the most direct and efficient methods for organoselenide synthesis. In this study, we report a highly regioselective Rh-catalyzed hydroselenation of unsymmetric 1,3-dienes, including internal unsymmetric dienes. This atom-economical method operates under mild conditions and selectively affords 3,4-Markovnikov products with excellent regiocontrol. The developed protocol was effective in reactions involving both internal and terminal dienes.

烯烃催化硒化反应是合成有机硒化物最直接、最有效的方法之一。在这项研究中，我们报道了一个高度区域选择性的铑催化的不对称的1,3-二烯的氢硒化反应，包括内部不对称的二烯。这种原子经济的方法在温和的条件下运行，选择性地提供3,4- markovnikov产物，具有良好的区域控制。开发的协议是有效的反应涉及内部和末端二烯。

引用次数: 0

Synergistic Ni/Co catalysis in C(sp2)–C(sp3) reductive coupling: a DFT study 协同Ni/Co催化C(sp2) -C （sp3）还原偶联：DFT研究

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-08-13 Epub Date: 2025-08-20 DOI: 10.1039/d5qo00975h

Junjie Liu , Fengjiao Xiao , Weichi Chen , Abing Duan

In nickel-catalyzed C(sp²)–C(sp³) cross-coupling, employing cost-effective cobalt complexes as co-catalysts presents distinct advantages. The Ni/Co dual-catalyzed reductive coupling of aryl halides and alkyls has emerged as a powerful strategy to form C(sp²)–C(sp³) bonds, yet its detailed mechanistic understanding remains elusive. Herein, we elucidate the mechanism for the reductive coupling between aryl and alkyl electrophiles in the presence of a Ni/Co^II(PC) dual catalytic system by density functional theory (DFT). The cobalt catalyst activates alkyl halides via an S_N2 oxidative addition pathway, generating a Co^III(Pc)-Alk intermediate, while the nickel catalyst specifically engages aryl halides. The subsequent anti-alkylation step between these intermediates drives the formation of C(sp²)–C(sp³) bonds with high selectivity. These mechanistic insights not only rationalize the enhanced efficiency and high functional-group compatibility of the Ni/Co system but also provide a framework for developing future dual-metal catalytic methodologies. Our findings advance synthetic strategies for constructing complex molecules and highlight the potential of bimetallic catalysis in organic synthesis.

在镍催化的C(sp2) -C （sp3）交叉偶联中，采用低成本的钴配合物作为共催化剂具有明显的优势。Ni/Co双催化芳基卤化物和烷基的还原偶联已成为形成C(sp2) -C （sp3）键的有力策略，但其详细机制尚不清楚。本文利用密度泛函理论（DFT）研究了Ni/CoII（PC）双催化体系下芳基和烷基亲电试剂之间的还原偶联机理。钴催化剂通过SN2氧化加成途径激活烷基卤化物，生成CoIII(Pc)-Alk中间体，而镍催化剂则专门作用于芳基卤化物。这些中间体之间随后的反烷基化步骤驱动形成具有高选择性的C(sp2) -C （sp3）键。这些机制的见解不仅使Ni/Co体系的效率提高和官能团相容性提高合理化，而且为发展未来的双金属催化方法提供了框架。我们的发现推进了构建复杂分子的合成策略，并突出了双金属催化在有机合成中的潜力。

{"title":"Synergistic Ni/Co catalysis in C(sp2)–C(sp3) reductive coupling: a DFT study","authors":"Junjie Liu , Fengjiao Xiao , Weichi Chen , Abing Duan","doi":"10.1039/d5qo00975h","DOIUrl":"10.1039/d5qo00975h","url":null,"abstract":"<div><div>In nickel-catalyzed C(sp<sup>2</sup>)–C(sp<sup>3</sup>) cross-coupling, employing cost-effective cobalt complexes as co-catalysts presents distinct advantages. The Ni/Co dual-catalyzed reductive coupling of aryl halides and alkyls has emerged as a powerful strategy to form C(sp<sup>2</sup>)–C(sp<sup>3</sup>) bonds, yet its detailed mechanistic understanding remains elusive. Herein, we elucidate the mechanism for the reductive coupling between aryl and alkyl electrophiles in the presence of a Ni/Co<sup>II</sup>(PC) dual catalytic system by density functional theory (DFT). The cobalt catalyst activates alkyl halides <em>via</em> an S<sub>N</sub>2 oxidative addition pathway, generating a Co<sup>III</sup>(Pc)-Alk intermediate, while the nickel catalyst specifically engages aryl halides. The subsequent anti-alkylation step between these intermediates drives the formation of C(sp<sup>2</sup>)–C(sp<sup>3</sup>) bonds with high selectivity. These mechanistic insights not only rationalize the enhanced efficiency and high functional-group compatibility of the Ni/Co system but also provide a framework for developing future dual-metal catalytic methodologies. Our findings advance synthetic strategies for constructing complex molecules and highlight the potential of bimetallic catalysis in organic synthesis.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 23","pages":"Pages 6506-6512"},"PeriodicalIF":0.0,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145533069","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}

引用次数: 0

The stereochemistry of substitution at S(vi) S（vi）取代的立体化学

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-08-13 Epub Date: 2025-08-20 DOI: 10.1039/d5qo01043h

Oliver L. Symes , James A. Bull

Since the re-birth of sulfur-fluoride exchange (SuFEx) chemistry, coined by Sharpless in 2014 as a ‘click’ reaction, the prevalence of sulfur(vi) moieties in medicinal, polymer and materials chemistry has increased significantly. SuFEx and analogous substitution reactions at electrophilic S(vi) reagents are often performed on symmetrical, achiral S(vi) centres. However, when these substitution reactions are applied to chiral S(vi) substrates, often enantioenriched chiral-at-sulfur aza-S(vi) analogues, the stereochemical outcome of the reaction must be considered to obtain the appropriate 3D configuration. In this review, we aim to draw together the stereochemical outcomes and mechanistic understanding of substitution reactions occurring at electrophilic chiral S(vi) reagents to provide support, and potential word of caution, to the growing field. In addition, we review the significant developments in stereocontrolled reactions at S(vi) centres.

自2014年由Sharpless创造的硫氟交换（SuFEx）化学（“点击”反应）重新诞生以来，硫（VI）基团在药物、聚合物和材料化学中的流行程度显著增加。亲电性S（VI）试剂上的SuFEx和类似取代反应通常在对称的非手性S（VI）中心进行。然而，当这些取代反应应用于手性S（VI）底物时，通常是对映体富集的手性-硫偶氮-S（VI）类似物，必须考虑反应的立体化学结果，以获得适当的三维构型。在这篇综述中，我们的目的是将发生在亲电性手性S（VI）试剂上的取代反应的立体化学结果和机理理解结合起来，为不断发展的领域提供支持和潜在的警告。此外，我们回顾了立体控制反应在S（VI）中心的重大进展。

引用次数: 0

Diastereoselective and enantioselective construction of 1,4-nonadjacent alkyne-tethered products through CuI-promoted deprotonation and addition of terminal alkynes 通过cui促进的去质子化和末端炔的加成，非相邻1,4炔系链产物的非立体和对映选择性构建

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-08-13 Epub Date: 2025-08-22 DOI: 10.1039/d5qo00995b

Jia-Le Zheng , Wan-Hong Yuan , Han-Wen Zheng , Wei Du , Ying-Chun Chen

While catalytic asymmetric alkynylation reactions have been extensively studied, the existing examples predominantly focus on the construction of the stereogenic center at the addition site. Here, we disclose a chiral Cu^I complex-catalysed asymmetric alkynylation reaction of prochiral terminal diynes, which can furnish a diverse array of products with remote alkyne-tethered 1,4-central chirality that is challenging to achieve. Mechanistic studies demonstrate that the initial desymmetrising deprotonation of the terminal diynes mediated by a chiral π-acidic Cu^I complex plays a crucial role in governing the diastereoselectivity, while the nucleophilic alkynylation step determines the enantiocontrol of the whole process. This strategy could be successfully extended to the kinetic transformation of racemic terminal alkynes. This stepwise asymmetric deprotonation and alkynylation strategy facilitated by a single chiral catalyst provides a robust platform for diastereo- and enantioselective construction of products with challenging-to-achieve rectilinear 1,4-central chirality.

催化不对称炔基化反应已经得到了广泛的研究，但现有的例子主要集中在加成位点的立体中心的构建上。本研究揭示了一种手性CuI配合物催化的前手性末端二炔的不对称烷基化反应，该反应可以提供多种具有远端烷基系链1,4中心手性的产品。机理研究表明，手性π-酸性CuI配合物介导的末端二炔初始去对称去质子化对非对映选择性起关键作用，而亲核炔基化则决定了整个过程的对映控制。该策略可以成功地推广到外消旋末端炔的动力学转化。这种由单手性催化剂促进的逐步不对称去质子化和烷基化策略为具有直链1,4中心手性的产品的非对映和对映选择性构建提供了强大的平台。

{"title":"Diastereoselective and enantioselective construction of 1,4-nonadjacent alkyne-tethered products through CuI-promoted deprotonation and addition of terminal alkynes","authors":"Jia-Le Zheng , Wan-Hong Yuan , Han-Wen Zheng , Wei Du , Ying-Chun Chen","doi":"10.1039/d5qo00995b","DOIUrl":"10.1039/d5qo00995b","url":null,"abstract":"<div><div>While catalytic asymmetric alkynylation reactions have been extensively studied, the existing examples predominantly focus on the construction of the stereogenic center at the addition site. Here, we disclose a chiral Cu<sup>I</sup> complex-catalysed asymmetric alkynylation reaction of prochiral terminal diynes, which can furnish a diverse array of products with remote alkyne-tethered 1,4-central chirality that is challenging to achieve. Mechanistic studies demonstrate that the initial desymmetrising deprotonation of the terminal diynes mediated by a chiral π-acidic Cu<sup>I</sup> complex plays a crucial role in governing the diastereoselectivity, while the nucleophilic alkynylation step determines the enantiocontrol of the whole process. This strategy could be successfully extended to the kinetic transformation of racemic terminal alkynes. This stepwise asymmetric deprotonation and alkynylation strategy facilitated by a single chiral catalyst provides a robust platform for diastereo- and enantioselective construction of products with challenging-to-achieve rectilinear 1,4-central chirality.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 23","pages":"Pages 6407-6414"},"PeriodicalIF":0.0,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144898833","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}

引用次数: 0

Expanding the silyl-Prins toolbox: selective access to C4-quaternary stereocenters in tetrahydropyrans using internal cyclopropylsilyl alcohols 扩展硅基普林斯工具箱：使用内部环丙基硅基醇选择性地获得四氢吡喃中的c4 -季立体中心

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-08-13 Epub Date: 2025-08-11 DOI: 10.1039/d5qo00984g

Paula González-Andrés , Alberto Cherubin , Asunción Barbero

Our ongoing research into silyl-Prins cyclizations has now provided a promising solution for the stereoselective synthesis of tetrahydropyrans bearing quaternary centers at C4. Building on the previous success with terminal cyclopropylsilyl alcohols, we now demonstrate that internal cyclopropylsilyl alcohols can also be effectively employed to construct highly substituted tetrahydropyrans. This new approach delivers products featuring both a quaternary center at C4 and a tertiary center at C6 with excellent stereocontrol. These findings not only broaden the scope of silyl-Prins cyclization but also establish a general and efficient strategy for accessing complex oxacyclic architectures with precise stereochemical outcomes.

我们正在进行的对硅基-普林斯环化的研究现在为立体选择性合成含C4四氢吡喃的四氢中心提供了一个有希望的解决方案。在先前成功的末端环丙基硅醇的基础上，我们现在证明了内部环丙基硅醇也可以有效地用于构建高取代的四氢吡喃。这种新方法提供的产品既具有C4的四级中心，又具有C6的三级中心，具有良好的立体控制能力。这些发现不仅拓宽了硅基-普林斯环化的范围，而且为获得具有精确立体化学结果的复杂无环结构建立了一种通用而有效的策略。

引用次数: 0

Streamlined synthesis of meta- or para-substituted triphenylamine[3]arenes and their hierarchical assembly into polyhedral cages 间或对取代三苯胺[3]芳烃的流线型合成及其在多面体笼中的分层组装

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-08-13 Epub Date: 2025-09-05 DOI: 10.1039/d5qo01089f

Wangjian Fang , Xin Li , Audrey Nathania Johan , Yimin Zhang , Guoqiang Jiang , Andrew C.-H. Sue

Triphenylamine[3]arenes (TPA[3]s) are a novel class of macrocyclic scaffolds with remarkable potential in supramolecular chemistry. In this study, we present a streamlined synthesis of TPA[3]s featuring meta- or para-substituted bromophenyl or ester moieties on the nitrogen-bridging units via a BF₃·Et₂O-catalysed one-pot Friedel–Crafts reaction, achieving up to near-quantitative yields within five minutes. These labile substituents at the equatorial positions enable efficient post-cyclisation functionalisation under mild conditions, facilitating the introduction of diverse functional groups, including nitrophenyl, pyrene, terpyridine, and carboxylic acid units. These meta-functionalised TPA[3]s exhibit exceptional structural flexibility, enabling their use as tri-topic building blocks for the construction of metal–organic cages (MOCs) through a subcomponent self-assembly strategy. By precisely tuning ligand denticity and metal coordination, we synthesised a diverse range of MOCs, including tetrahedral M₄L₄ cages, dimeric M₃L₂ assemblies, and octahedral M₆L₄ architectures. These results demonstrate the versatility of TPA[3] scaffolds in advancing hierarchical supramolecular assembly and highlight their potential for creating structurally diverse and well-defined supramolecular architectures.

三苯胺[3]-芳烃（TPA[3] -芳烃）是一类新型的大环支架，在超分子化学领域具有显著的应用潜力。在这项研究中，我们通过BF3•et20催化的一锅Friedel-Crafts反应，在5分钟内获得了接近定量的产率，在氮桥单元上具有间位或对取代的溴苯基或酯基团的TPA bbb50的流线型合成。这些位于赤道位置的不稳定取代基能够在温和的条件下实现高效的环化后功能化，促进了各种官能团的引入，包括硝基苯、芘、三联吡啶和羧酸单位。这些元功能化的TPA[3]具有特殊的结构灵活性，使其能够通过子组件自组装策略用作构建金属有机笼（moc）的三主题构建块。通过精确调整配体密度和金属配位，我们合成了多种moc，包括四面体M4L4笼，二聚体M3L2组装体和八面体M6L4结构。这些结果证明了TPA[3]支架在推进分层超分子组装方面的多功能性，并突出了它们在创建结构多样化和定义良好的超分子结构方面的潜力。

{"title":"Streamlined synthesis of meta- or para-substituted triphenylamine[3]arenes and their hierarchical assembly into polyhedral cages","authors":"Wangjian Fang , Xin Li , Audrey Nathania Johan , Yimin Zhang , Guoqiang Jiang , Andrew C.-H. Sue","doi":"10.1039/d5qo01089f","DOIUrl":"10.1039/d5qo01089f","url":null,"abstract":"<div><div>Triphenylamine[3]arenes (TPA[3]s) are a novel class of macrocyclic scaffolds with remarkable potential in supramolecular chemistry. In this study, we present a streamlined synthesis of TPA[3]s featuring <em>meta</em>- or <em>para</em>-substituted bromophenyl or ester moieties on the nitrogen-bridging units <em>via</em> a BF<sub>3</sub>·Et<sub>2</sub>O-catalysed one-pot Friedel–Crafts reaction, achieving up to near-quantitative yields within five minutes. These labile substituents at the equatorial positions enable efficient post-cyclisation functionalisation under mild conditions, facilitating the introduction of diverse functional groups, including nitrophenyl, pyrene, terpyridine, and carboxylic acid units. These <em>meta</em>-functionalised TPA[3]s exhibit exceptional structural flexibility, enabling their use as tri-topic building blocks for the construction of metal–organic cages (MOCs) through a subcomponent self-assembly strategy. By precisely tuning ligand denticity and metal coordination, we synthesised a diverse range of MOCs, including tetrahedral M<sub>4</sub>L<sub>4</sub> cages, dimeric M<sub>3</sub>L<sub>2</sub> assemblies, and octahedral M<sub>6</sub>L<sub>4</sub> architectures. These results demonstrate the versatility of TPA[3] scaffolds in advancing hierarchical supramolecular assembly and highlight their potential for creating structurally diverse and well-defined supramolecular architectures.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 23","pages":"Pages 6594-6601"},"PeriodicalIF":0.0,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144995653","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}

引用次数: 0

Divergent synthesis of two polycyclic frameworks containing tricyclic bridgehead carbon centers by gold-catalyzed cycloisomerization of o-cyclopropylidenemethyl-o′-alkynylbiaryls 金催化邻环丙基甲基-o′-炔基二芳基环异构化合成含三环桥头堡碳中心的两个多环框架

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-08-13 Epub Date: 2025-08-26 DOI: 10.1039/d5qo00816f

Lucía Sánchez-Jiménez , Adrián Gargantiel , Manuel A. Fernández-Rodríguez , Patricia García-García

Compounds containing tricyclic bridgehead carbon centers are privileged structures in drug discovery. In this work, two different polycyclic scaffolds containing this substructure have been accessed by divergent gold-catalyzed cycloisomerizations of o-cyclopropylidenemethyl-o′-alkynylbiaryls. Selectivity towards one or the other scaffold is mainly controlled by temperature. The electronic nature of the arene group at the alkyne also plays a significant role, which is explained based on the proposed mechanism.

含有三环桥头堡碳中心的化合物是药物发现中的优势结构。在这项工作中，含有该亚结构的两种不同的多环支架已经通过不同的金催化的o-环丙基甲基-o ' -炔基二芳基的环异构化得到。对一种或另一种支架的选择性主要由温度控制。炔上芳烃基团的电子性质也起着重要的作用，这是根据所提出的机理来解释的。

引用次数: 0

Structurally divergent reactivity of 2,2-disubstituted azetidines – mechanistic insights and stereochemical implications of amide coupling and ring expansion to 5,6-dihydro-4H-1,3-oxazines 2,2-二取代氮杂啶的结构发散性——酰胺偶联和扩环对5,6-二氢- 4h -1,3-恶嗪的机理和立体化学意义

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-08-13 Epub Date: 2025-08-28 DOI: 10.1039/d5qo00804b

Aditya K. Sahay , Callum S. Begg , Xiurong Zhang , James. A. Bull , Alan C. Spivey

Azetidines have gained traction in drug discovery for their ability to introduce conformational constraint and modulate physiochemical properties. Strategies that enable their selective functionalization or controlled expansion into more complex scaffolds provide opportunities for molecular diversification to rapidly access new chemical space. Subjecting 2,2-disubstituted azetidines to amide coupling with carboxylic acids is found to effect either N-acylation or ring expansion to spiro and 6,6-disubstituted 5,6-dihydro-4H-1,3-oxazine, dependent on reaction conditions. A diverse range of topologically interesting heterocycles, which hold significant potential for pharmaceutical screening, have been prepared using this divergent reaction manifold. A mechanistic framework, supported by additive screening and trapping experiments, is presented to account for the ring expansion and racemization that accompanies these transformations when the substrate allows formation of a ring-opened azafulvenium intermediate.

氮杂啶因其引入构象约束和调节物理化学性质的能力而在药物发现中获得了吸引力。使其选择性功能化或控制扩展成更复杂支架的策略为分子多样化/新的化学空间提供了机会。研究发现，将2,2-二取代氮杂啶与羧酸进行酰胺偶联，根据反应条件的不同，会对螺旋和6,6 -二取代5,6-二氢- 4h -1,3-恶嗪产生n -酰化或扩环作用。利用这种发散反应歧管制备了各种各样的拓扑上有趣的杂环，这些杂环具有很大的药物筛选潜力。在添加剂筛选和捕获实验的支持下，提出了一个机制框架，以解释当底物允许形成开环的azafulvenium中间体时，伴随这些转化的环扩展和外消旋化

{"title":"Structurally divergent reactivity of 2,2-disubstituted azetidines – mechanistic insights and stereochemical implications of amide coupling and ring expansion to 5,6-dihydro-4H-1,3-oxazines","authors":"Aditya K. Sahay , Callum S. Begg , Xiurong Zhang , James. A. Bull , Alan C. Spivey","doi":"10.1039/d5qo00804b","DOIUrl":"10.1039/d5qo00804b","url":null,"abstract":"<div><div>Azetidines have gained traction in drug discovery for their ability to introduce conformational constraint and modulate physiochemical properties. Strategies that enable their selective functionalization or controlled expansion into more complex scaffolds provide opportunities for molecular diversification to rapidly access new chemical space. Subjecting 2,2-disubstituted azetidines to amide coupling with carboxylic acids is found to effect either <em>N</em>-acylation or ring expansion to spiro and 6,6-disubstituted 5,6-dihydro-4<em>H</em>-1,3-oxazine, dependent on reaction conditions. A diverse range of topologically interesting heterocycles, which hold significant potential for pharmaceutical screening, have been prepared using this divergent reaction manifold. A mechanistic framework, supported by additive screening and trapping experiments, is presented to account for the ring expansion and racemization that accompanies these transformations when the substrate allows formation of a ring-opened azafulvenium intermediate.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 23","pages":"Pages 6556-6563"},"PeriodicalIF":0.0,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144911120","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}

引用次数: 0

Photocatalytic ketone synthesis: recent advances in radical-based approaches from carboxylic acids and derivatives 光催化酮合成：羧酸及其衍生物自由基基合成方法的最新进展

Organic chemistry frontiers : an international journal of organic chemistry

Pub Date : 2025-08-13 Epub Date: 2025-08-14 DOI: 10.1039/d5qo01059d

Shengbiao Yang , Xiaochen Wang , Lan Bao , Tianzhen Wang , Lingang Wu , Qingmin Wang

Ketones are widely recognized as privileged structural motifs in organic synthesis due to their unique dual reactivity profile, serving as versatile electrophiles in numerous carbon–carbon and carbon–heteroatom bond-forming transformations. Their ubiquitous presence in pharmacologically active compounds, advanced materials, and agrochemicals further underscores their synthetic importance. Consequently, the design of novel catalytic platforms enabling efficient construction of structurally diverse ketones from readily available precursors represents a significant challenge in contemporary synthetic methodology. Carboxylic acids and derivatives, owing to their natural abundance, low cost, and exceptional structural variability, are an ideal class of starting materials for such transformations. The integration of these compounds with photocatalysis enables their transformation into ketones through radical-based reaction strategies, offering distinct advantages over conventional two-electron reaction systems by circumventing their inherent limitations.

酮类由于其独特的双反应性而被广泛认为是有机合成中的特殊结构基序，在许多碳-碳和碳杂原子成键转化中作为通用亲电试剂。它们在药理活性化合物、先进材料和农用化学品中的普遍存在进一步强调了它们在合成中的重要性。因此，新型催化平台的设计能够从现成的前体中高效地构建结构多样化的酮，这是当代合成方法中的一个重大挑战。羧酸及其衍生物，由于其天然丰度、低成本和特殊的结构可变性，代表了这类转化的理想起始材料。这些化合物与光催化的整合使得它们能够通过基于自由基的反应策略转化为酮，通过规避其固有的局限性，提供了比传统的双电子反应系统明显的优势。

{"title":"Photocatalytic ketone synthesis: recent advances in radical-based approaches from carboxylic acids and derivatives","authors":"Shengbiao Yang , Xiaochen Wang , Lan Bao , Tianzhen Wang , Lingang Wu , Qingmin Wang","doi":"10.1039/d5qo01059d","DOIUrl":"10.1039/d5qo01059d","url":null,"abstract":"<div><div>Ketones are widely recognized as privileged structural motifs in organic synthesis due to their unique dual reactivity profile, serving as versatile electrophiles in numerous carbon–carbon and carbon–heteroatom bond-forming transformations. Their ubiquitous presence in pharmacologically active compounds, advanced materials, and agrochemicals further underscores their synthetic importance. Consequently, the design of novel catalytic platforms enabling efficient construction of structurally diverse ketones from readily available precursors represents a significant challenge in contemporary synthetic methodology. Carboxylic acids and derivatives, owing to their natural abundance, low cost, and exceptional structural variability, are an ideal class of starting materials for such transformations. The integration of these compounds with photocatalysis enables their transformation into ketones through radical-based reaction strategies, offering distinct advantages over conventional two-electron reaction systems by circumventing their inherent limitations.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 23","pages":"Pages 6662-6680"},"PeriodicalIF":0.0,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144840267","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}

引用次数: 0

首页上一页

类型

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

数据库

全部 ACS Publications Elsevier ieeexplore Springer The Royal Society of Chemistry Wiley

期刊

Organic chemistry frontiers : an international journal of organic chemistry

全部 Acc. Chem. Res. ACS Applied Bio Materials ACS Appl. Electron. Mater. ACS Appl. Energy Mater. ACS Appl. Mater. Interfaces ACS Appl. Nano Mater. ACS Appl. Polym. Mater. ACS BIOMATER-SCI ENG ACS Catal. ACS Cent. Sci. ACS Chem. Biol. ACS Chemical Health & Safety ACS Chem. Neurosci. ACS Comb. Sci. ACS Earth Space Chem. ACS Energy Lett. ACS Infect. Dis. ACS Macro Lett. ACS Mater. Lett. ACS Med. Chem. Lett. ACS Nano ACS Omega ACS Photonics ACS Sens. ACS Sustainable Chem. Eng. ACS Synth. Biol. Anal. Chem. BIOCHEMISTRY-US Bioconjugate Chem. BIOMACROMOLECULES Chem. Res. Toxicol. Chem. Rev. Chem. Mater. CRYST GROWTH DES ENERG FUEL Environ. Sci. Technol. Environ. Sci. Technol. Lett. Eur. J. Inorg. Chem. IND ENG CHEM RES Inorg. Chem. J. Agric. Food. Chem. J. Chem. Eng. Data J. Chem. Educ. J. Chem. Inf. Model. J. Chem. Theory Comput. J. Med. Chem. J. Nat. Prod. J PROTEOME RES J. Am. Chem. Soc. LANGMUIR MACROMOLECULES Mol. Pharmaceutics Nano Lett. Org. Lett. ORG PROCESS RES DEV ORGANOMETALLICS J. Org. Chem. J. Phys. Chem. J. Phys. Chem. A J. Phys. Chem. B J. Phys. Chem. C J. Phys. Chem. Lett. Analyst Anal. Methods Biomater. Sci. Catal. Sci. Technol. Chem. Commun. Chem. Soc. Rev. CHEM EDUC RES PRACT CRYSTENGCOMM Dalton Trans. Energy Environ. Sci. ENVIRON SCI-NANO ENVIRON SCI-PROC IMP ENVIRON SCI-WAT RES Faraday Discuss. Food Funct. Green Chem. Inorg. Chem. Front. Integr. Biol. J. Anal. At. Spectrom. J. Mater. Chem. A J. Mater. Chem. B J. Mater. Chem. C Lab Chip Mater. Chem. Front. Mater. Horiz. MEDCHEMCOMM Metallomics Mol. Biosyst. Mol. Syst. Des. Eng. Nanoscale Nanoscale Horiz. Nat. Prod. Rep. New J. Chem. Org. Biomol. Chem. Org. Chem. Front. PHOTOCH PHOTOBIO SCI PCCP Polym. Chem.

﹀