Beilstein Journal of Organic Chemistry最新文献

Concise trichlorination of methyl ketones using sodium hypochlorite pentahydrate. 用五水次氯酸钠对甲基酮进行简明三氯化。

IF 2.7 4区化学

Beilstein Journal of Organic Chemistry Pub Date : 2026-10-08 eCollection Date: 2026-01-01 DOI: 10.3762/bjoc.22.113

Ayumu Sakai, Takumi Tanaka, Takahiro Hosokawa, Takumi Kawai, Hideyuki Tsutsui, Yoshikazu Kimura, Shinobu Takizawa, Masayuki Kirihara

{"title":"Concise trichlorination of methyl ketones using sodium hypochlorite pentahydrate.","authors":"Ayumu Sakai, Takumi Tanaka, Takahiro Hosokawa, Takumi Kawai, Hideyuki Tsutsui, Yoshikazu Kimura, Shinobu Takizawa, Masayuki Kirihara","doi":"10.3762/bjoc.22.113","DOIUrl":"https://doi.org/10.3762/bjoc.22.113","url":null,"abstract":"We report a practical and efficient method for the synthesis of trichloromethyl ketones from the corresponding methyl ketones via a two-step sequence involving trifluoroacetylation followed by selective chlorination. The key chlorination step proceeds under mild, weakly acidic conditions using sodium hypochlorite pentahydrate, thus avoiding the use of hazardous chlorine gas or strong bases. A wide range of aromatic and aliphatic methyl ketones was successfully converted into the corresponding trichloromethyl ketones in high yields. Mechanistic studies suggest that the reaction involves the formation of a 2,2-dichloro-1,3-diketone intermediate and subsequent cleavage of the trifluoroacetyl group. In contrast to previously reported base-mediated halogenation methods, the present protocol exhibits a high regioselectivity and operational simplicity under acidic conditions. This method provides a convenient alternative for the synthesis of trichloromethyl ketones from readily available substrates and is expected to be broadly applicable in organic synthesis and medicinal chemistry.","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"22 ","pages":"1385-1391"},"PeriodicalIF":2.7,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13656031/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149179230","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Hidden aromaticity behind paratropic ring currents in oxoverdazyl and benzotriazinyl radicals. 氧苄唑基和苯并三嗪基自由基中异向环电流背后隐藏的芳香性。

IF 2.7 4区化学

Beilstein Journal of Organic Chemistry Pub Date : 2026-10-07 eCollection Date: 2026-01-01 DOI: 10.3762/bjoc.22.111

Rinat F Salikov, Alexander Yu Belyy, Yury V Tomilov

{"title":"Hidden aromaticity behind paratropic ring currents in oxoverdazyl and benzotriazinyl radicals.","authors":"Rinat F Salikov, Alexander Yu Belyy, Yury V Tomilov","doi":"10.3762/bjoc.22.111","DOIUrl":"https://doi.org/10.3762/bjoc.22.111","url":null,"abstract":"Monoradicals occupy a theoretically underdetermined state in aromaticity theory, possessing both aromatic (2n + 1) and antiaromatic (2n) spin populations. We systematically investigate benzotriazinyl and oxoverdazyl radicals by disentangling their energetic and magnetic aromaticity through isodesmic reactions, NICS calculations, and EDDB analysis. Our results reveal that both systems are energetically aromatic, yet sustain paratropic ring currents, revealing the divergence of energetic and magnetic criteria. EDDB analysis unveils the electronic origin of this divergence: the antiaromatic α-spins with the unpaired electron are largely localized, whereas the aromatic β-spins are extensively delocalized within the heterocyclic rings. This spin-specific localization provides a direct electronic rationale for the observed dichotomy and contributes to the refinement of Mandado's electron rule for odd-electron systems, demonstrating that the two spin populations influence energetic and magnetic properties differently. Oxidation and reduction of the parent radicals lead to convergence of these criteria in closed-shell ions, offering insights into their reversible redox behavior. This study provides a quantitative framework for understanding aromaticity in odd-electron species.","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"22 ","pages":"1376-1381"},"PeriodicalIF":2.7,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13656023/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149179246","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Design and synthesis of bioactive molecules. 生物活性分子的设计与合成。

IF 2.7 4区化学

Beilstein Journal of Organic Chemistry Pub Date : 2026-10-07 eCollection Date: 2026-01-01 DOI: 10.3762/bjoc.22.112

Fengzhi Zhang, David R Spring

引用次数: 0

Properties and applications of [n]cumulenes. [n]聚酰亚胺的性质及应用。

IF 2.7 4区化学

Beilstein Journal of Organic Chemistry Pub Date : 2026-10-02 eCollection Date: 2026-01-01 DOI: 10.3762/bjoc.22.110

Julio César Hernández-Camacho, José Enrique Barquera-Lozada

引用次数: 0

Bifunctional ligand-enabled gold-catalyzed cycloisomerization of 2'-ethynylbiaryl-2-yl carbonyl compounds. 2′-乙基二芳基-2基羰基化合物的双功能配体催化环异构化。

IF 2.7 4区化学

Beilstein Journal of Organic Chemistry Pub Date : 2026-10-01 eCollection Date: 2026-01-01 DOI: 10.3762/bjoc.22.109

Matthew Shapiro, Carlos D Quintanilla, Liming Zhang

{"title":"Bifunctional ligand-enabled gold-catalyzed cycloisomerization of 2'-ethynylbiaryl-2-yl carbonyl compounds.","authors":"Matthew Shapiro, Carlos D Quintanilla, Liming Zhang","doi":"10.3762/bjoc.22.109","DOIUrl":"10.3762/bjoc.22.109","url":null,"abstract":"Gold(I) vinylidenes are powerful yet typically fleeting electrophiles whose synthetic exploitation has, until now, relied largely on two strategies: 1,2-migration of a halide or silyl group from a gold-activated alkyne, or dual gold catalysis of diyne substrates. Here, we introduce a ligand-enabled catalytic entry to these reactive intermediates based on a prior stoichiometric approach reported by Fürstner. A bifunctional biaryl-2-ylphosphine bearing a remote N,N-dialkylamide group promotes in situ formation of a gold acetylide without an external base; the proton thereby relayed to the amide acts as an internal Brønsted acid that activates a tethered carbonyl, triggering 6-exo cyclization to a putative gold(I) vinylidene. The catalysis converts 2'-ethynylbiaryl-2-yl aldehydes and ketones into synthetically valuable phenanthrene-9-carbaldehydes under mild conditions. In contrast to the observed decarbonylation in the stoichiometric case, the bifunctional ligand is proposed to promote facile protodeauration of an acylgold intermediate, thereby preserving the valuable aldehyde moiety in the products. The transformation accommodates a range of electronic environments and is moderately tolerant of steric demand, underscoring metal-ligand cooperation as a valuable approach to accessing and harnessing gold vinylidenes.","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"22 ","pages":"1351-1357"},"PeriodicalIF":2.7,"publicationDate":"2026-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13635906/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149103436","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Expanded use of benzamidines in the Groebke-Blackburn-Bienaymé synthesis of imidazoles and their biological evaluation. 苯并脒在groebke - blackburn - bienaym<s:1>咪唑合成中的扩大使用及其生物学评价。

IF 2.7 4区化学

Beilstein Journal of Organic Chemistry Pub Date : 2026-09-30 eCollection Date: 2026-01-01 DOI: 10.3762/bjoc.22.108

Kamryn Walker, Sydney Rivas, Erik Tillman-Smith, Kayla McLeod, Jeanee Bullock, Jacqueline Smith

{"title":"Expanded use of benzamidines in the Groebke-Blackburn-Bienaymé synthesis of imidazoles and their biological evaluation.","authors":"Kamryn Walker, Sydney Rivas, Erik Tillman-Smith, Kayla McLeod, Jeanee Bullock, Jacqueline Smith","doi":"10.3762/bjoc.22.108","DOIUrl":"https://doi.org/10.3762/bjoc.22.108","url":null,"abstract":"Heterocyclic compounds are often considered privileged scaffolds because many bioactive molecules contain these moieties. Several inhibitors of the valosin-containing protein (VCP, also known as p97), a target for cancer therapeutics, contain 5 or 6-membered heterocyclic cores. With the rise of resistance among these VCP inhibitors, we propose a new class of heterocycles as potential cancer therapeutics. The Groebke-Blackburn-Bienaymé (GBB) reaction is a classic method to produce imidazole compounds. In our earlier study, we showed that acyclic amidines can effectively produce trisubstituted imidazoles known as benzyl imine tricyclic imidazoles (BITIs) via this multicomponent reaction. Herein, we report the first systematic evaluation of para-substituted benzamidines produced via the microwave-assisted GBB reaction, which enables the tuning of trisubstituted imidazole compounds and their application as VCP inhibitors. Several of the newly developed compounds inhibit VCP activity, with one amidinopyridine derivative showing low-micromolar, cancer-selective cytotoxicity. This establishes a new scaffold for VCP inhibitor development.","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"22 ","pages":"1344-1350"},"PeriodicalIF":2.7,"publicationDate":"2026-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13635903/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149103500","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Homogeneous copper-catalyzed aerobic oxidation of alcohols and aldehydes: mechanistic insights and recent advances. 均相铜催化醇和醛的有氧氧化：机理的见解和最新进展。

IF 2.7 4区化学

Beilstein Journal of Organic Chemistry Pub Date : 2026-09-29 eCollection Date: 2026-01-01 DOI: 10.3762/bjoc.22.107

Hristo Petkov, Svilen P Simeonov

{"title":"Homogeneous copper-catalyzed aerobic oxidation of alcohols and aldehydes: mechanistic insights and recent advances.","authors":"Hristo Petkov, Svilen P Simeonov","doi":"10.3762/bjoc.22.107","DOIUrl":"https://doi.org/10.3762/bjoc.22.107","url":null,"abstract":"Copper-catalyzed aerobic oxidation of alcohols and aldehydes has become a key transformation for the sustainable synthesis of carbonyl compounds, combining high efficiency with the use of molecular oxygen as a benign terminal oxidant. Owing to its earth-abundance, low cost, low toxicity, and versatile redox properties, copper offers a compelling alternative to traditional noble metal catalysts and stoichiometric oxidation methods. This review highlights the evolution of copper-catalyzed aerobic oxidation of alcohols, emphasizing two distinct mechanistic regimes: nitroxyl radical-mediated systems and nitroxyl-free pathways, in which copper-ligand complexes directly promote dioxygen activation and substrate oxidation. Methods for conversion of aldehydes to carboxylic acids were also discussed. Apart from historical overview of the considered protocols, recent advances in the field were deliberated. Despite significant progress, the development of simpler, mediator-free catalytic systems based on readily available reagents remains a central challenge and a promising direction for future research.","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"22 ","pages":"1323-1343"},"PeriodicalIF":2.7,"publicationDate":"2026-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13635905/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149103432","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Synthesis of spiro-1,2-dihydropyridine derivatives via cycloisomerization of 3-aza-1,5-enynes catalyzed by gold(I) complex/polyoxometalate hybrids. 金(I)配合物/多金属氧酸盐杂化催化3-叠氮-1,5-烯环异构化合成螺-1,2-二氢吡啶衍生物。

IF 2.7 4区化学

Beilstein Journal of Organic Chemistry Pub Date : 2026-09-28 eCollection Date: 2026-01-01 DOI: 10.3762/bjoc.22.106

Titien Simon, Fabian Schlimpen, Pierre de Frémont, Stefan Chassaing, Aurélien Blanc

引用次数: 0

Photochemical strategies in divalent samarium catalysis. 二价钐催化的光化学策略。

IF 2.7 4区化学

Beilstein Journal of Organic Chemistry Pub Date : 2026-09-25 eCollection Date: 2026-01-01 DOI: 10.3762/bjoc.22.105

Takahito Kuribara, Tetsuhiro Nemoto

引用次数: 0

Silver-catalyzed anionic [3 + 2] cycloaddition of benzyl isocyanides with polyfluoroalkylchromones and pyrones: direct synthesis of 2-arylpyrroles. 银催化苯基异氰酸酯与多氟烷基铬酮和吡咯酮的阴离子[3 + 2]环加成：2-芳基吡咯的直接合成。

IF 2.7 4区化学

Beilstein Journal of Organic Chemistry Pub Date : 2026-09-23 eCollection Date: 2026-01-01 DOI: 10.3762/bjoc.22.103

Ivan A Kochnev, Alexey Yu Barkov

{"title":"Silver-catalyzed anionic [3 + 2] cycloaddition of benzyl isocyanides with polyfluoroalkylchromones and pyrones: direct synthesis of 2-arylpyrroles.","authors":"Ivan A Kochnev, Alexey Yu Barkov","doi":"10.3762/bjoc.22.103","DOIUrl":"10.3762/bjoc.22.103","url":null,"abstract":"A silver-catalyzed anionic [3 + 2] cycloaddition of benzyl isocyanides has been developed, providing direct one-pot access to 2-arylpyrroles - a privileged scaffold pervasive in medicinal chemistry and functional materials. Despite high demand, general one-step routes to this motif remain rare, and the synthetic potential of benzyl isocyanides in cycloaddition chemistry has been severely limited by their low reactivity. We herein show that the combination of AgOAc (10 mol %) and KOt-Bu efficiently promote the reaction of benzyl isocyanides with 2-polyfluoroalkylchromones and 6-(trifluoromethyl)-4H-pyrones, delivering 2-arylpyrroles in yields of up to 83% with complete chemo- and regioselectivity. The protocol is operationally simple and extends readily to chromones and pyrones lacking a trifluoromethyl group, demonstrating a broad substrate scope. This work establishes a practical catalytic entry to an important heterocyclic class and unlocks the underexplored utility of benzyl isocyanides in cycloaddition reactions.","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"22 ","pages":"1284-1294"},"PeriodicalIF":2.7,"publicationDate":"2026-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13618341/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149073204","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0