首页 > 最新文献

Organic Letters最新文献

英文 中文
Batch and Continuous-Flow Electrochemical Geminal Difluorination of Indeno[1,2-c]furans. 茚并[1,2-c]呋喃的间歇和连续流电化学双氟化反应。
IF 4.9 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-19 Epub Date: 2024-07-05 DOI: 10.1021/acs.orglett.4c02235
Guo-Cai Yuan, Fang-Ling Gao, Kang-Wei Liu, Minggang Li, Yuqi Lin, Ke-Yin Ye

An electrochemical gem-difluorination of indeno[1,2-c]furans using commercially available and easy-to-use triethylamine trihydrofluoride as both the electrolyte and fluorinating agent was developed. Remarkably, different reaction pathways of indeno[1,2-c]furans, i.e., paired electrolysis and net oxidation, are operative in a batch reactor and a continuous-flow microreactor to afford the corresponding gem-difluorinated indanones and indenones, respectively.

本研究开发了一种茚并[1,2-c]呋喃的电化学宝石二氟化反应,其电解质和氟化剂均为市售且易于使用的三乙胺三氢氟酸。值得注意的是,茚并[1,2-c]呋喃的不同反应途径,即配对电解和净氧化,可在间歇反应器和连续流微反应器中分别进行,从而得到相应的宝石二氟化茚酮和茚酮。
{"title":"Batch and Continuous-Flow Electrochemical Geminal Difluorination of Indeno[1,2-<i>c</i>]furans.","authors":"Guo-Cai Yuan, Fang-Ling Gao, Kang-Wei Liu, Minggang Li, Yuqi Lin, Ke-Yin Ye","doi":"10.1021/acs.orglett.4c02235","DOIUrl":"10.1021/acs.orglett.4c02235","url":null,"abstract":"<p><p>An electrochemical <i>gem</i>-difluorination of indeno[1,2-<i>c</i>]furans using commercially available and easy-to-use triethylamine trihydrofluoride as both the electrolyte and fluorinating agent was developed. Remarkably, different reaction pathways of indeno[1,2-<i>c</i>]furans, i.e., paired electrolysis and net oxidation, are operative in a batch reactor and a continuous-flow microreactor to afford the corresponding <i>gem</i>-difluorinated indanones and indenones, respectively.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":null,"pages":null},"PeriodicalIF":4.9,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141537186","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Catalyst-Free, Zn-Mediated Decarboxylative Coupling of Chlorostibines to Access Alkylstibines with Stable C(sp3)-Sb Bonds. 无催化剂、锌介导的氯代二苯乙烯脱羧偶联,获得具有稳定 C(sp3)-Sb 键的烷基二苯乙烯。
IF 4.9 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-19 Epub Date: 2024-07-05 DOI: 10.1021/acs.orglett.4c02132
Liyuan Le, Huifan Zeng, Wenjun Zhou, Niu Tang, Shuang-Feng Yin, Nobuaki Kambe, Renhua Qiu

Herein, decarboxylative C(sp3)-Sb coupling of aliphatic carboxylic acid derivatives with chlorostibines to access alkylstibines has been achieved. This catalyst-, ligand-, and base-free approach using zinc as a reductant affords various kinds of benzyldiarylstibines and other monoalkyldiarylstibines and tolerates various functional groups, including chlorine, bromine, hydroxyl, amide, sulfone, and cyano groups. The late-stage modification and the gram-scale experiments illustrate its potential application.

在此,我们实现了脂肪族羧酸衍生物与氯代二苯乙烯的脱羧 C(sp3)-Sb 偶联,从而获得烷基二苯乙烯。这种以锌为还原剂的无催化剂、无配体、无碱的方法可以得到各种苄基二芳基丝氨酸和其他单烷基二芳基丝氨酸,并可容忍各种官能团,包括氯、溴、羟基、酰胺、砜和氰基。后期改性和克级实验说明了它的潜在应用价值。
{"title":"Catalyst-Free, Zn-Mediated Decarboxylative Coupling of Chlorostibines to Access Alkylstibines with Stable C(sp<sup>3</sup>)-Sb Bonds.","authors":"Liyuan Le, Huifan Zeng, Wenjun Zhou, Niu Tang, Shuang-Feng Yin, Nobuaki Kambe, Renhua Qiu","doi":"10.1021/acs.orglett.4c02132","DOIUrl":"10.1021/acs.orglett.4c02132","url":null,"abstract":"<p><p>Herein, decarboxylative C(sp<sup>3</sup>)-Sb coupling of aliphatic carboxylic acid derivatives with chlorostibines to access alkylstibines has been achieved. This catalyst-, ligand-, and base-free approach using zinc as a reductant affords various kinds of benzyldiarylstibines and other monoalkyldiarylstibines and tolerates various functional groups, including chlorine, bromine, hydroxyl, amide, sulfone, and cyano groups. The late-stage modification and the gram-scale experiments illustrate its potential application.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":null,"pages":null},"PeriodicalIF":4.9,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141537187","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Site-Selective Photobromination of O-Acetylated Carbohydrates in Benzotrifluoride. 三氟甲苯中 O-乙酰化碳水化合物的位点选择性光溴化作用。
IF 4.9 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-19 Epub Date: 2024-07-08 DOI: 10.1021/acs.orglett.4c01898
Guoqing Zhang, Nicholas W See, Norbert Wimmer, Michael J Godinez, Scott A Cameron, Richard H Furneaux, Vito Ferro

Ferrier photobromination enables direct synthetic access to valuable 5-C-bromosugars but has limitations that restrict its broader use. The reaction is typically conducted in CCl4 heated at reflux with irradiation by broad spectrum, energy-inefficient heat lamps. Herein, we demonstrate that the reaction proceeds rapidly and efficiently with PhCF3 as a safe and environmentally benign alternative to CCl4 at mild temperatures (≤40 °C) inside a compact photoreactor fitted with purple light-emitting diodes (LEDs).

Ferrier 光溴化反应可以直接合成有价值的 5-C 溴糖,但其局限性限制了它的广泛应用。该反应通常在 CCl4 中进行,加热回流,并用光谱宽、能效低的加热灯照射。在这里,我们证明了在装有紫色发光二极管(LED)的紧凑型光反应器中,使用 PhCF3 作为 CCl4 的安全环保替代品,可以在温和的温度下(≤40 °C)快速高效地进行反应。
{"title":"Site-Selective Photobromination of <i>O</i>-Acetylated Carbohydrates in Benzotrifluoride.","authors":"Guoqing Zhang, Nicholas W See, Norbert Wimmer, Michael J Godinez, Scott A Cameron, Richard H Furneaux, Vito Ferro","doi":"10.1021/acs.orglett.4c01898","DOIUrl":"10.1021/acs.orglett.4c01898","url":null,"abstract":"<p><p>Ferrier photobromination enables direct synthetic access to valuable 5-<i>C</i>-bromosugars but has limitations that restrict its broader use. The reaction is typically conducted in CCl<sub>4</sub> heated at reflux with irradiation by broad spectrum, energy-inefficient heat lamps. Herein, we demonstrate that the reaction proceeds rapidly and efficiently with PhCF<sub>3</sub> as a safe and environmentally benign alternative to CCl<sub>4</sub> at mild temperatures (≤40 °C) inside a compact photoreactor fitted with purple light-emitting diodes (LEDs).</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":null,"pages":null},"PeriodicalIF":4.9,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141553625","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Stereoselective Electrophilic Sulfenylation of β,β-Disubstituted Enesulfinamides: Asymmetric Construction of Less Accessible Acyclic α,α-Disubstituted α-Sulfenylated Ketimines. β,β-二取代烯磺酰胺的立体选择性亲电磺酰化:不对称构建较难获得的环状α,α-二取代α-亚磺酰基酮亚胺。
IF 4.9 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-19 Epub Date: 2024-07-05 DOI: 10.1021/acs.orglett.4c02030
Nuermaimaiti Yisimayili, Zheng-Fei Li, Tao Liu, Chong-Dao Lu

Current methods for the asymmetric α-sulfenylation of carbonyls cannot be applied to acyclic carbonyls that have two similar substituents at the α-position. This research demonstrated that the electrophilic sulfenylation of geometry-defined acyclic β,β-disubstituted enesulfinamides using S-aryl or S-alkyl benzenethiosulfonates can be highly stereoselective. This process results in enantioenriched α,α-disubstituted α-sulfenylated ketone surrogates with sulfur-containing acyclic tetrasubstituted carbon stereocenters bearing two electronically and sterically similar substituents (e.g., methyl and ethyl). Furthermore, by employing the corresponding stereoisomers of enensulfinamides, any of the four stereoisomers of α-sulfenylated ketimines can be selectively accessed.

目前对羰基进行不对称α-亚磺酰化的方法无法应用于在α位有两个类似取代基的无环羰基。这项研究证明,使用 S-芳基或 S-烷基苯硫代磺酸盐对几何定义的无环 β、β-二取代烯磺酰胺进行亲电烯丙基磺化反应具有很高的立体选择性。这一工艺可得到对映体富集的α,α-二取代α-亚磺酰化酮替代物,其含硫无环四取代碳立体中心带有两个电子和立体相似的取代基(如甲基和乙基)。此外,通过使用相应的烯磺酰胺立体异构体,可以选择性地获得α-亚磺酰化酮的四种立体异构体中的任何一种。
{"title":"Stereoselective Electrophilic Sulfenylation of β,β-Disubstituted Enesulfinamides: Asymmetric Construction of Less Accessible Acyclic α,α-Disubstituted α-Sulfenylated Ketimines.","authors":"Nuermaimaiti Yisimayili, Zheng-Fei Li, Tao Liu, Chong-Dao Lu","doi":"10.1021/acs.orglett.4c02030","DOIUrl":"10.1021/acs.orglett.4c02030","url":null,"abstract":"<p><p>Current methods for the asymmetric α-sulfenylation of carbonyls cannot be applied to acyclic carbonyls that have two similar substituents at the α-position. This research demonstrated that the electrophilic sulfenylation of geometry-defined acyclic β,β-disubstituted enesulfinamides using <i>S</i>-aryl or <i>S</i>-alkyl benzenethiosulfonates can be highly stereoselective. This process results in enantioenriched α,α-disubstituted α-sulfenylated ketone surrogates with sulfur-containing acyclic tetrasubstituted carbon stereocenters bearing two electronically and sterically similar substituents (e.g., methyl and ethyl). Furthermore, by employing the corresponding stereoisomers of enensulfinamides, any of the four stereoisomers of α-sulfenylated ketimines can be selectively accessed.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":null,"pages":null},"PeriodicalIF":4.9,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532855","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Rapid Construction of Polycyclic Skeletons via Brønsted-Base-Catalyzed Annulations of Ethylidene 1,3-Indenediones and Vinyl 1,2-Diketones. 通过 Brønsted 碱催化亚乙基 1,3-Indenediones 和乙烯基 1,2-Diketones 的环化反应快速构建多环骨架。
IF 4.9 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-19 Epub Date: 2024-07-09 DOI: 10.1021/acs.orglett.4c01690
Lixuan Zhu, Haotian Luo, Jinggong Liu, Benlong Luo, Shuang Yang, Xinqiang Fang

Brønsted-base-catalyzed diversified annulations between ethylidene 1,3-indenediones and vinyl 1,2-diketones have been achieved, delivering three types of products containing oxabicyclo[3.2.1]octane, spiro[4.5]decane, and branched triquinane skeletons, respectively, which widely exist in natural products and bioactive substances. Two unprecedented reaction modes have been disclosed, and the reactions could be readily scaled up. The protocol shows the potential of 1,2-diketone-mediated reactions in the rapid construction of complicated polycyclic scaffolds.

在布氏碱催化下,亚乙基 1,3-茚与乙烯基 1,2-二酮实现了多样化环化反应,生成了三种分别含有氧杂双环[3.2.1]辛烷、螺[4.5]癸烷和支链三喹烷骨架的产物,这些产物广泛存在于天然产物和生物活性物质中。该研究揭示了两种前所未有的反应模式,而且这些反应很容易放大。该方案显示了 1,2-二酮介导的反应在快速构建复杂多环支架方面的潜力。
{"title":"Rapid Construction of Polycyclic Skeletons via Brønsted-Base-Catalyzed Annulations of Ethylidene 1,3-Indenediones and Vinyl 1,2-Diketones.","authors":"Lixuan Zhu, Haotian Luo, Jinggong Liu, Benlong Luo, Shuang Yang, Xinqiang Fang","doi":"10.1021/acs.orglett.4c01690","DOIUrl":"10.1021/acs.orglett.4c01690","url":null,"abstract":"<p><p>Brønsted-base-catalyzed diversified annulations between ethylidene 1,3-indenediones and vinyl 1,2-diketones have been achieved, delivering three types of products containing oxabicyclo[3.2.1]octane, spiro[4.5]decane, and branched triquinane skeletons, respectively, which widely exist in natural products and bioactive substances. Two unprecedented reaction modes have been disclosed, and the reactions could be readily scaled up. The protocol shows the potential of 1,2-diketone-mediated reactions in the rapid construction of complicated polycyclic scaffolds.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":null,"pages":null},"PeriodicalIF":4.9,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141557382","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Telescoping a Prenyltransferase and a Diterpene Synthase to Transform Unnatural FPP Derivatives to Diterpenoids. 通过延长异戊烯基转移酶和二萜合成酶将非天然 FPP 衍生物转化为二萜。
IF 4.9 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-19 Epub Date: 2024-07-08 DOI: 10.1021/acs.orglett.4c01670
Henry Struwe, Heng Li, Finn Schrödter, Laurent Höft, Jörg Fohrer, Jeroen S Dickschat, Andreas Kirschning

New diterpenoids are accessible from non-natural FPP derivatives as substrates for an enzymatic elongation cyclization cascade using the geranylgeranyl pyrophosphate synthase (GGPPS) from Streptomyces cyaneofuscatus and the spata-13,17-diene synthase (SpS) from Streptomyces xinghaiensis. This approach led to four new biotransformation products including three new cyclododecane cores and a macrocyclic ether. For the first time, a 1,12-terpene cyclization was observed when shifting the central olefinic double bond toward the geminial methyl groups creating a nonconjugated 1,4-diene.

通过使用来自链霉菌 Cyofuscatus 的香叶基丙酮焦磷酸合成酶(GGPPS)和来自星海链霉菌的 spata-13,17-dene 合成酶(SpS)进行酶促伸长环化级联,可以从非天然 FPP 衍生物中获得新的二萜类化合物作为底物。这种方法产生了四种新的生物转化产物,包括三种新的环十二烷核心和一种大环醚。在将中心烯烃双键移向geminial甲基时,首次观察到了1,12-三萜环化现象,产生了非共轭的1,4-二烯。
{"title":"Telescoping a Prenyltransferase and a Diterpene Synthase to Transform Unnatural FPP Derivatives to Diterpenoids.","authors":"Henry Struwe, Heng Li, Finn Schrödter, Laurent Höft, Jörg Fohrer, Jeroen S Dickschat, Andreas Kirschning","doi":"10.1021/acs.orglett.4c01670","DOIUrl":"10.1021/acs.orglett.4c01670","url":null,"abstract":"<p><p>New diterpenoids are accessible from non-natural FPP derivatives as substrates for an enzymatic elongation cyclization cascade using the geranylgeranyl pyrophosphate synthase (GGPPS) from <i>Streptomyces cyaneofuscatus</i> and the spata-13,17-diene synthase (SpS) from <i>Streptomyces xinghaiensis</i>. This approach led to four new biotransformation products including three new cyclododecane cores and a macrocyclic ether. For the first time, a 1,12-terpene cyclization was observed when shifting the central olefinic double bond toward the geminial methyl groups creating a nonconjugated 1,4-diene.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":null,"pages":null},"PeriodicalIF":4.9,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141557384","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Copper-Catalyzed Dual Remote Asymmetric Vinylogous Alkynylallylic Substitution of Yne-Allylic Esters with Coumarins. 铜催化香豆素与炔烯丙基酯的双远程不对称炔烯丙基烷基取代。
IF 4.9 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-19 DOI: 10.1021/acs.orglett.4c02199
Xin-Ru Wang, Meng-Die Li, Zi-Han Wang, Hui Zhu, Jia-Run Wang, Ying-Ying Wei, Tao-Yan Lin

Chiral coumarins and their derivatives are ubiquitous structural motifs found in an array of biologically and therapeutically active natural products and drugs. Herein, a highly enantioselective dual remote copper-catalyzed vinylogous alkynylallylic substitution of yne-allylic esters with coumarins has been developed. The practicality of this method is exemplified by the use of readily available starting materials; mild reaction conditions; excellent regio-, enantio-, and stereoselectivities; and the very broad substrate scope (67 examples), while the scalability and further applications of this method are illustrated by the gram-scale reaction and the series of derivations of the products.

{"title":"Copper-Catalyzed Dual Remote Asymmetric Vinylogous Alkynylallylic Substitution of Yne-Allylic Esters with Coumarins.","authors":"Xin-Ru Wang, Meng-Die Li, Zi-Han Wang, Hui Zhu, Jia-Run Wang, Ying-Ying Wei, Tao-Yan Lin","doi":"10.1021/acs.orglett.4c02199","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c02199","url":null,"abstract":"<p><p>Chiral coumarins and their derivatives are ubiquitous structural motifs found in an array of biologically and therapeutically active natural products and drugs. Herein, a highly enantioselective dual remote copper-catalyzed vinylogous alkynylallylic substitution of yne-allylic esters with coumarins has been developed. The practicality of this method is exemplified by the use of readily available starting materials; mild reaction conditions; excellent regio-, enantio-, and stereoselectivities; and the very broad substrate scope (67 examples), while the scalability and further applications of this method are illustrated by the gram-scale reaction and the series of derivations of the products.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":null,"pages":null},"PeriodicalIF":4.9,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141726596","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Photocatalytic Proficiency of Cinnoline Moiety for Cross-Coupling Reactions: A Two in One Photocatalyst. 噌啉分子在交叉偶联反应中的光催化能力:二合一光催化剂。
IF 4.9 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-19 Epub Date: 2024-07-03 DOI: 10.1021/acs.orglett.4c01812
Rashmi Prakash, Partha Pratim Sen, Vishali Pathania, Sudipta Raha Roy

Herein, we have developed a new class of organic photocatalysts that can mimic transition metals for several oxidative and reductive organic cross-coupling transformations. Due to its wide potential window in both the oxidation and reduction ranges, cinnoline exhibits dual catalytic activity under visible light illumination, acting as both a photoreductant and photooxidant.

在此,我们开发了一类新型有机光催化剂,它可以模拟过渡金属,用于多种氧化和还原有机交叉偶联转化。由于噌啉在氧化和还原范围内都具有宽广的潜力窗口,因此它在可见光照射下具有双重催化活性,既是光还原剂,又是光氧化剂。
{"title":"Photocatalytic Proficiency of Cinnoline Moiety for Cross-Coupling Reactions: A Two in One Photocatalyst.","authors":"Rashmi Prakash, Partha Pratim Sen, Vishali Pathania, Sudipta Raha Roy","doi":"10.1021/acs.orglett.4c01812","DOIUrl":"10.1021/acs.orglett.4c01812","url":null,"abstract":"<p><p>Herein, we have developed a new class of organic photocatalysts that can mimic transition metals for several oxidative and reductive organic cross-coupling transformations. Due to its wide potential window in both the oxidation and reduction ranges, cinnoline exhibits dual catalytic activity under visible light illumination, acting as both a photoreductant and photooxidant.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":null,"pages":null},"PeriodicalIF":4.9,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141490019","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
A Configurationally Stable Helical Indenofluorene. 一种构型稳定的螺旋茚芴。
IF 4.9 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-19 Epub Date: 2024-07-05 DOI: 10.1021/acs.orglett.4c02128
Álvaro Martínez-Pinel, Luis Lezama, Juan M Cuerva, Raquel Casares, Víctor Blanco, Carlos M Cruz, Alba Millán

We report the synthesis and study of the optoelectronic, magnetic, and chiroptical properties of a helically chiral diradicaloid based on dibenzoindeno[2,1-c]fluorene. The molecule shows a small HOMO-LUMO gap and a moderate singlet-triplet gap, which agrees with the results of DFT calculations. The helical structure of the compound, confirmed by X-ray diffraction, is configurationally stable, which allows the isolation of both enantiomers and the evaluation of the chiroptical properties (ECD).

我们报告了一种基于二苯并茚并[2,1-c]芴的螺旋手性二维类化合物的合成及其光电、磁性和气光性质研究。该分子显示出较小的 HOMO-LUMO 间隙和适度的单线-三线间隙,这与 DFT 计算的结果一致。经 X 射线衍射证实,该化合物的螺旋结构在构型上是稳定的,因此可以分离出两种对映体并评估其气光性质(ECD)。
{"title":"A Configurationally Stable Helical Indenofluorene.","authors":"Álvaro Martínez-Pinel, Luis Lezama, Juan M Cuerva, Raquel Casares, Víctor Blanco, Carlos M Cruz, Alba Millán","doi":"10.1021/acs.orglett.4c02128","DOIUrl":"10.1021/acs.orglett.4c02128","url":null,"abstract":"<p><p>We report the synthesis and study of the optoelectronic, magnetic, and chiroptical properties of a helically chiral diradicaloid based on dibenzoindeno[2,1-<i>c</i>]fluorene. The molecule shows a small HOMO-LUMO gap and a moderate singlet-triplet gap, which agrees with the results of DFT calculations. The helical structure of the compound, confirmed by X-ray diffraction, is configurationally stable, which allows the isolation of both enantiomers and the evaluation of the chiroptical properties (ECD).</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":null,"pages":null},"PeriodicalIF":4.9,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532791","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Exploring the Explosive Potential: Synthesis and Characterization of Ring-Fused Oxadiazolo[3,4-b]pyrazine 1-Oxide Polymorphs with Balanced Energetic Properties. 探索爆炸潜力:具有平衡能量特性的环融噁二唑并[3,4-b]吡嗪 1-氧化物多晶体的合成与表征。
IF 4.9 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-19 Epub Date: 2024-07-08 DOI: 10.1021/acs.orglett.4c02116
Abhishek Kumar Yadav, Rimpi Devi, Vikas D Ghule, Srinivas Dharavath

A novel fused-ring compound, 5-azido-6-oxo-6,7-dihydro-[1,2,5]oxadiazolo[3,4-b]pyrazine 1-oxide (3a), was synthesized for the first time with simple two-step process and characterized using various spectroscopic techniques such NMR, IR, EA and HRMS. Two polymorphs (α-3a and β-3a) identified by SCXRD differ in crystal packing and noncovalent interactions, demonstrating high density, substantial heat of formation, and superior detonation properties with reduced mechanical sensitivity compared to TNT, TATB, and close to RDX, suggesting their potential as environmentally friendly high energy density materials.

本研究首次采用简单的两步法合成了一种新型熔环化合物--5-叠氮-6-氧代-6,7-二氢-[1,2,5]噁二唑并[3,4-b]吡嗪 1-氧化物(3a),并利用 NMR、IR、EA 和 HRMS 等多种光谱技术对其进行了表征。通过 SCXRD 鉴定出的两种多晶型(α-3a 和 β-3a)在晶体堆积和非共价相互作用方面存在差异,与 TNT 和 TATB 相比,它们具有高密度、高形成热和优异的引爆性能,同时机械敏感性降低,接近 RDX,这表明它们具有作为环境友好型高能量密度材料的潜力。
{"title":"Exploring the Explosive Potential: Synthesis and Characterization of Ring-Fused Oxadiazolo[3,4-<i>b</i>]pyrazine 1-Oxide Polymorphs with Balanced Energetic Properties.","authors":"Abhishek Kumar Yadav, Rimpi Devi, Vikas D Ghule, Srinivas Dharavath","doi":"10.1021/acs.orglett.4c02116","DOIUrl":"10.1021/acs.orglett.4c02116","url":null,"abstract":"<p><p>A novel fused-ring compound, 5-azido-6-oxo-6,7-dihydro-[1,2,5]oxadiazolo[3,4-<i>b</i>]pyrazine 1-oxide (<b>3a</b>), was synthesized for the first time with simple two-step process and characterized using various spectroscopic techniques such NMR, IR, EA and HRMS. Two polymorphs (<b>α-3a</b> and <b>β-3a</b>) identified by SCXRD differ in crystal packing and noncovalent interactions, demonstrating high density, substantial heat of formation, and superior detonation properties with reduced mechanical sensitivity compared to TNT, TATB, and close to RDX, suggesting their potential as environmentally friendly high energy density materials.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":null,"pages":null},"PeriodicalIF":4.9,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141553623","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
期刊
Organic Letters
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.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
现在去查看 取消
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术
文献互助 智能选刊 最新文献 互助须知 联系我们:info@booksci.cn
Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。
Copyright © 2023 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1