Pub Date : 2024-11-01DOI: 10.1016/j.tet.2024.134354
Javier Ordóñez-Hernández, Fernanda Ferrusca-Martínez, Arturo Jiménez-Sánchez
Lipid droplets (LDs) are ubiquitous intracellular organelles present in various cell types, ranging from adipocytes to cancer cells. Despite their involvement in numerous diseases, current methodologies for monitoring LD dynamics rely primarily on static imaging with a limited selection of fluorescent dyes. In this study, we introduce two novel BODIPY-derived fluorophores designed to facilitate real-time monitoring of LD dynamics. By incorporating triphenylamino (TPA) moieties into the BODIPY core both asymmetrically and symmetrically, we modulated the fluorescence response to the green (GFP) and deep-red (Cy5) confocal channels, respectively, thus allowing dual-channel fluorescence capability for high-resolution, dynamic imaging of LDs within live cells, providing new insights into their behavior.
{"title":"BODIPY-derived fluorescent probes for targeting and tracking lipid droplets dynamics","authors":"Javier Ordóñez-Hernández, Fernanda Ferrusca-Martínez, Arturo Jiménez-Sánchez","doi":"10.1016/j.tet.2024.134354","DOIUrl":"10.1016/j.tet.2024.134354","url":null,"abstract":"<div><div>Lipid droplets (LDs) are ubiquitous intracellular organelles present in various cell types, ranging from adipocytes to cancer cells. Despite their involvement in numerous diseases, current methodologies for monitoring LD dynamics rely primarily on static imaging with a limited selection of fluorescent dyes. In this study, we introduce two novel BODIPY-derived fluorophores designed to facilitate real-time monitoring of LD dynamics. By incorporating triphenylamino (TPA) moieties into the BODIPY core both asymmetrically and symmetrically, we modulated the fluorescence response to the green (GFP) and deep-red (Cy5) confocal channels, respectively, thus allowing dual-channel fluorescence capability for high-resolution, dynamic imaging of LDs within live cells, providing new insights into their behavior.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"168 ","pages":"Article 134354"},"PeriodicalIF":2.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142654180","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The Brook Rearrangement holds significant applications in organic synthesis and has been investigated extensively in past decades. Among the various types of Brook rearrangements, catalytic versions have gained increased attention from the chemical community due to their superior control over stereoselectivity and high reaction efficiency. This review provides a comprehensive summary of recent examples of transition metal-promoted Brook rearrangement and related reactions. It encompasses copper-catalyzed migration of a silyl or boryl group, which represents the most intensively studied reactions, along with zinc-promoted reactions and other transition metal-catalyzed reactions. The substrate scope and reaction mechanisms of these examples are meticulously detailed and analyzed.
{"title":"Transition metal promoted Brook rearrangement and its related reactions","authors":"Fazhou Yang, Jinbao Wang, Yujie Dong, Nianci Zhang, Cheng Zhang","doi":"10.1016/j.tet.2024.134351","DOIUrl":"10.1016/j.tet.2024.134351","url":null,"abstract":"<div><div>The Brook Rearrangement holds significant applications in organic synthesis and has been investigated extensively in past decades. Among the various types of Brook rearrangements, catalytic versions have gained increased attention from the chemical community due to their superior control over stereoselectivity and high reaction efficiency. This review provides a comprehensive summary of recent examples of transition metal-promoted Brook rearrangement and related reactions. It encompasses copper-catalyzed migration of a silyl or boryl group, which represents the most intensively studied reactions, along with zinc-promoted reactions and other transition metal-catalyzed reactions. The substrate scope and reaction mechanisms of these examples are meticulously detailed and analyzed.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"168 ","pages":"Article 134351"},"PeriodicalIF":2.1,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142578727","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-31DOI: 10.1016/j.tet.2024.134334
José G. Becerra-González , Eduardo Peña-Cabrera , José L. Belmonte-Vázquez
BODIPYs (Boron-dipyrromethenes) are a class of fluorophores widely used in a plethora of scientific applications in material science and biomedicine due to their exceptional optical properties. The modulation of the absorption and emission wavelengths of BODIPYs is an area with significant growth opportunities, allowing these compounds to be tailored for specific applications. This review addresses different synthetic strategies that could modify their electronic and optical properties of the BODIPY core, mainly the absorption and emission wavelengths (λabs = 422 nm - λemis = 753 nm and quantum yields up to Φc-hex = 100 %). These methodologies include reactions like nucleophilic substitutions with (chiral/achiral) primary and secondary amines, alkyl/aryl alcohols, active methylenes, as well as Liebeskind-Srogl, Sonogashira, Heck, and Suzuki cross-coupling reactions at the meso and peripheral positions of the BODIPY core. These synthetic strategies incorporate specific functional groups that influence the π-system conjugation, generation of AIEgens, and Donor-Acceptor (D-A) or Donor-Acceptor-Donor (D-A-D) architectures, enabling the labeling of biomolecules such as estrone and tyrosine.
{"title":"From blue to red. Reaching the full visible spectrum with a single fluorophore: BODIPY","authors":"José G. Becerra-González , Eduardo Peña-Cabrera , José L. Belmonte-Vázquez","doi":"10.1016/j.tet.2024.134334","DOIUrl":"10.1016/j.tet.2024.134334","url":null,"abstract":"<div><div>BODIPYs (Boron-dipyrromethenes) are a class of fluorophores widely used in a plethora of scientific applications in material science and biomedicine due to their exceptional optical properties. The modulation of the absorption and emission wavelengths of BODIPYs is an area with significant growth opportunities, allowing these compounds to be tailored for specific applications. This review addresses different synthetic strategies that could modify their electronic and optical properties of the BODIPY core, mainly the absorption and emission wavelengths (λ<sub>abs</sub> = 422 nm - λ<sub>emis</sub> = 753 nm and quantum yields up to Φ<sub>c-hex</sub> = 100 %). These methodologies include reactions like nucleophilic substitutions with (chiral/achiral) primary and secondary amines, alkyl/aryl alcohols, active methylenes, as well as Liebeskind-Srogl, Sonogashira, Heck, and Suzuki cross-coupling reactions at the <em>meso</em> and peripheral positions of the BODIPY core. These synthetic strategies incorporate specific functional groups that influence the π-system conjugation, generation of AIEgens, and Donor-Acceptor (D-A) or Donor-Acceptor-Donor (D-A-D) architectures, enabling the labeling of biomolecules such as estrone and tyrosine.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"168 ","pages":"Article 134334"},"PeriodicalIF":2.1,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142654181","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-30DOI: 10.1016/j.tet.2024.134349
Akrti Sharma, Mangalampalli Ravikanth
The β-arylated meso-tetra(p-tolyl) triphyrins[2.1.1] containing two, three, and four p-fluorophenyl groups were synthesized by reacting appropriate β-bromo triphyrin[2.1.1] with p-fluorophenyl boronic acid in toluene/THF/H2O (1:1:1) at 80 οC for 8 h–12 h and their properties were compared with our previously reported β-arylated triphyrins[2.1.1] containing one and six p-fluorophenyl groups. The increase of the number of p-fluorophenyl groups at the β-pyrrole carbons induces steric hindrance at the periphery of triphyrin[2.1.1] that results in the alteration of electronic properties due to distortion in the macrocycle which is reflected in their structure, spectral and redox properties. The X-ray structure analysis revealed that β-di(p-fluorophenyl) meso-tetra(p-tolyl) triphyrin[2.1.1] was almost planar like meso-tetra(phenyl) triphyrin[2.1.1] whereas the β-hexa(p-fluorophenyl) meso-tetra(p-tolyl) triphyrin[2.1.1] was significantly distorted. The absorption spectra of β-arylated triphyrins[2.1.1] showed bathochromically shifted Soret and Q-bands with reduction in absorption coefficients and increase in the bandwidth compared to the β-unsubstituted meso-tetra(p-tolyl) triphyrin[2.1.1] and the maximum effects were noted for β-hexa(p-fluorophenyl) meso-tetra(p-tolyl) triphyrin[2.1.1]. The β-arylated meso-tetra(p-tolyl) triphyrins[2.1.1] are stable under electrochemical conditions and DFT/TD-DFT studies are in agreement with the experimental observations.
{"title":"Synthesis and properties of β-arylated triphyrins[2.1.1] by successive introduction of one to six aryl groups at the β-pyrrole carbons","authors":"Akrti Sharma, Mangalampalli Ravikanth","doi":"10.1016/j.tet.2024.134349","DOIUrl":"10.1016/j.tet.2024.134349","url":null,"abstract":"<div><div>The <em>β</em>-arylated <em>meso</em>-tetra(<em>p</em>-tolyl) triphyrins[2.1.1] containing two, three, and four <em>p</em>-fluorophenyl groups were synthesized by reacting appropriate <em>β</em>-bromo triphyrin[2.1.1] with <em>p</em>-fluorophenyl boronic acid in toluene/THF/H<sub>2</sub>O (1:1:1) at 80 <sup>ο</sup>C for 8 h–12 h and their properties were compared with our previously reported <em>β</em>-arylated triphyrins[2.1.1] containing one and six <em>p</em>-fluorophenyl groups. The increase of the number of <em>p</em>-fluorophenyl groups at the <em>β</em>-pyrrole carbons induces steric hindrance at the periphery of triphyrin[2.1.1] that results in the alteration of electronic properties due to distortion in the macrocycle which is reflected in their structure, spectral and redox properties. The X-ray structure analysis revealed that <em>β</em>-di(<em>p</em>-fluorophenyl) <em>meso</em>-tetra(<em>p</em>-tolyl) triphyrin[2.1.1] was almost planar like <em>meso</em>-tetra(phenyl) triphyrin[2.1.1] whereas the <em>β</em>-hexa(<em>p</em>-fluorophenyl) <em>meso</em>-tetra(<em>p</em>-tolyl) triphyrin[2.1.1] was significantly distorted. The absorption spectra of <em>β</em>-arylated triphyrins[2.1.1] showed bathochromically shifted Soret and Q-bands with reduction in absorption coefficients and increase in the bandwidth compared to the <em>β</em>-unsubstituted <em>meso</em>-tetra(<em>p</em>-tolyl) triphyrin[2.1.1] and the maximum effects were noted for <em>β</em>-hexa(<em>p</em>-fluorophenyl) <em>meso</em>-tetra(<em>p</em>-tolyl) triphyrin[2.1.1]. The <em>β</em>-arylated <em>meso</em>-tetra(<em>p</em>-tolyl) triphyrins[2.1.1] are stable under electrochemical conditions and DFT/TD-DFT studies are in agreement with the experimental observations.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"168 ","pages":"Article 134349"},"PeriodicalIF":2.1,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142572173","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-29DOI: 10.1016/j.tet.2024.134337
Salma E. Mora-Rodríguez , Selene Lagunas-Rivera , J. Merced Martínez-Rosales , Yolanda Alcaraz-Contreras , Jorge Alberto Mendoza-Pérez , Miguel A. Vázquez
This research introduces a heterogeneous approach utilizing a resin-bound sulfonic acid catalyst (Dowex®-H) to synthesize benzo[f]indole-4,9-dione derivatives using β-enaminones systems and 2-bromonaphtoquinone. This method facilitates synthesizing a diverse range of compounds with varying substitution patterns, achieving yields of 88 %. The catalyst can be reused for up to five cycles without requiring reactivation. These compounds absorption spectra also show absorption (λmax) around 250–260 nm with a significant transition around 400 nm. Their photocatalytic potential was assessed by the model reaction of benzylamine photooxidation, achieving a yield of over 99 % within 36 h.
{"title":"Heterogeneous synthesis of benzo[f]indole-4,9-diones derivatives using sulfonic resin and photocatalytic study","authors":"Salma E. Mora-Rodríguez , Selene Lagunas-Rivera , J. Merced Martínez-Rosales , Yolanda Alcaraz-Contreras , Jorge Alberto Mendoza-Pérez , Miguel A. Vázquez","doi":"10.1016/j.tet.2024.134337","DOIUrl":"10.1016/j.tet.2024.134337","url":null,"abstract":"<div><div>This research introduces a heterogeneous approach utilizing a resin-bound sulfonic acid catalyst (Dowex®-H) to synthesize benzo[<em>f</em>]indole-4,9-dione derivatives using β-enaminones systems and 2-bromonaphtoquinone. This method facilitates synthesizing a diverse range of compounds with varying substitution patterns, achieving yields of 88 %. The catalyst can be reused for up to five cycles without requiring reactivation. These compounds absorption spectra also show absorption (<em>λ</em><sub>max</sub>) around 250–260 nm with a significant transition around 400 nm. Their photocatalytic potential was assessed by the model reaction of benzylamine photooxidation, achieving a yield of over 99 % within 36 h.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"168 ","pages":"Article 134337"},"PeriodicalIF":2.1,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142572171","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
We developed an efficient mechanochemical method for the synthesis of 1,2-dihydropyridine derivatives from push-pull enamines and tert-propargyl alcohols under ball milling with p-TsOH/HFIP. The reaction proceeds smoothly under metal-free conditions with fast, efficient, and high-yielding synthesis of 1,2-dihydropyridines. The reaction shows excellent atom economy, with a broad substrate generality.
{"title":"Mechanochemical cyclization of push-pull enamines with propargyl alcohols","authors":"Srinivasarao Yaragorla, Megavath Vinod, Dandugula Sneha Latha","doi":"10.1016/j.tet.2024.134339","DOIUrl":"10.1016/j.tet.2024.134339","url":null,"abstract":"<div><div>We developed an efficient mechanochemical method for the synthesis of 1,2-dihydropyridine derivatives from push-pull enamines and <em>tert</em>-propargyl alcohols under ball milling with <em>p</em>-TsOH/HFIP. The reaction proceeds smoothly under metal-free conditions with fast, efficient, and high-yielding synthesis of 1,2-dihydropyridines. The reaction shows excellent atom economy, with a broad substrate generality.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"168 ","pages":"Article 134339"},"PeriodicalIF":2.1,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142578731","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-29DOI: 10.1016/j.tet.2024.134336
Zuleyma Martínez-Campos , Francisco José Palacios-Can , Susana T. López-Cortina , Rodrigo Said Razo-Hernández , Mario Fernández-Zertuche
In this work, we report the synthesis of three series of 3,5-disubstituted isoxazoles (4a-d, 5a-d and 6a-d), as analogues of the clinically important drug baclofen. The isoxazole ring systems were assembled through the key copper-catalyzed 1,3-dipolar cycloaddition reaction between a nitrile oxide (generated in situ from nitro compounds) and an alkyne. An X-ray crystallography study shows that the 1,3-dipolar cycloaddition reactions proceeded with very high regioselectively, leading exclusively to the formation of the 3,5-disubstituted regio isomers. Additionally, it was possible to obtain these compounds in enantiomerically pure form using SuperQuat-type chiral auxiliary. As suggested by our QSAR analysis and docking studies, these analogues have the potential to be biologically active as GABAB receptor modulators. Finally, the absorption, distribution, properties of metabolism and excretion (ADME) of the synthesized molecules was also determined by a computational approach. From this work we obtained five molecules ((S)-4d, (S)-5b, (S)-6b, (S)-6c and (S)-6d) as potential GABAB receptor agonists.
{"title":"Design and synthesis of 3,5-disubstituted isoxazoles by Cu-mediated 1,3-dipolar cycloaddition and their in silico evaluation as potential GABAB receptor modulators","authors":"Zuleyma Martínez-Campos , Francisco José Palacios-Can , Susana T. López-Cortina , Rodrigo Said Razo-Hernández , Mario Fernández-Zertuche","doi":"10.1016/j.tet.2024.134336","DOIUrl":"10.1016/j.tet.2024.134336","url":null,"abstract":"<div><div>In this work, we report the synthesis of three series of 3,5-disubstituted isoxazoles (<strong>4a-d</strong>, <strong>5a-d</strong> and <strong>6a-d</strong>), as analogues of the clinically important drug baclofen. The isoxazole ring systems were assembled through the key copper-catalyzed 1,3-dipolar cycloaddition reaction between a nitrile oxide (generated <em>in situ</em> from nitro compounds) and an alkyne. An X-ray crystallography study shows that the 1,3-dipolar cycloaddition reactions proceeded with very high regioselectively, leading exclusively to the formation of the 3,5-disubstituted regio isomers. Additionally, it was possible to obtain these compounds in enantiomerically pure form using SuperQuat-type chiral auxiliary. As suggested by our QSAR analysis and docking studies, these analogues have the potential to be biologically active as GABA<sub>B</sub> receptor modulators. Finally, the absorption, distribution, properties of metabolism and excretion (ADME) of the synthesized molecules was also determined by a computational approach. From this work we obtained five molecules ((<em>S</em>)-<strong>4d</strong>, (<em>S</em>)-<strong>5b</strong>, (<em>S</em>)-<strong>6b</strong>, (<em>S</em>)-<strong>6c</strong> and (<em>S</em>)-<strong>6d</strong>) as potential GABA<sub>B</sub> receptor agonists.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"168 ","pages":"Article 134336"},"PeriodicalIF":2.1,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142578730","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-29DOI: 10.1016/j.tet.2024.134345
Chuan Wu , Li-Rong Han , Jin-Song Hou , Qing-Han Li
A simple and mild catalytic SN2′-type displacement of propargyl halides with organotitanium reagents is reported. The SN2′-type displacement of propargyl bromides with organotitanium reagents mediated by CuI (2 mol%)/MePPh2(4 mol%) in dichloro methane afforded multi-substituted allenes in good yields (up to 95 %) at 40 °C for 5 h. The aryls bearing electron-donating or electron-withdrawing groups in aryltitanium reagents gave multi-substituted allenes in good yields. In addition, the di-substituted allenes bearing a naphthyl group was obtained in 54–99 % selectivities with isolated yields of 43–83 %. The process was simple and easily performed, and it provides an efficient method for the synthesis of di-substituted allene derivatives. On the basis of the experimental results, a possible catalytic cycle has been proposed.
报告了一种简单温和的有机钛试剂催化 SN2′型置换丙炔卤化物的方法。在二氯甲烷中，以 CuI (2 mol%)/MePPh2(4 mol%)为介导，在 40 °C 下催化 5 小时，丙炔基溴化物与有机钛试剂发生 SN2′型置换反应，得到了多取代烯。此外，带有萘基的二取代烯烃的选择性为 54-99%，分离产率为 43-83%。该工艺简单易行，为合成二取代烯烃衍生物提供了一种有效的方法。根据实验结果，提出了一种可能的催化循环。
{"title":"Highly efficient synthesis of di-substituted allenes via copper-catalyzed SN2′- substitution reaction of organotitanium reagents with propargyl bromides","authors":"Chuan Wu , Li-Rong Han , Jin-Song Hou , Qing-Han Li","doi":"10.1016/j.tet.2024.134345","DOIUrl":"10.1016/j.tet.2024.134345","url":null,"abstract":"<div><div>A simple and mild catalytic S<sub>N</sub>2′-type displacement of propargyl halides with organotitanium reagents is reported. The S<sub>N</sub>2′-type displacement of propargyl bromides with organotitanium reagents mediated by CuI (2 mol%)/MePPh<sub>2</sub>(4 mol%) in dichloro methane afforded multi-substituted allenes in good yields (up to 95 %) at 40 °C for 5 h. The aryls bearing electron-donating or electron-withdrawing groups in aryltitanium reagents gave multi-substituted allenes in good yields. In addition, the di-substituted allenes bearing a naphthyl group was obtained in 54–99 % selectivities with isolated yields of 43–83 %. The process was simple and easily performed, and it provides an efficient method for the synthesis of di-substituted allene derivatives. On the basis of the experimental results, a possible catalytic cycle has been proposed.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"168 ","pages":"Article 134345"},"PeriodicalIF":2.1,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142654179","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-29DOI: 10.1016/j.tet.2024.134344
Alexander D. Roth, Zhazira Koldasbay, Brett H. Ford, Khaidar Kairbek, Heejoon Ahn, Tarini S. Hardikar, Katherine M. Lane, Sarah M. Haynes, Dasan M. Thamattoor
Various 9,10-cyclopropanated phenanthrenes have been shown previously to be viable photochemical precursors to many different types of carbenes. There is also one known example in the literature of a related approach used to generate diphenylketene from a phenanthrene-derived cyclobutanone in a laser flash photolysis study. In an effort to broaden the scope of this promising yet under-utilized method of ketene generation, the synthesis and characterization of several phenanthrene-based cyclobutanones, and their subsequent photolysis to produce a variety of ketenes, are presented in this report. The ketenes are produced, along with phenanthrene, by a formal 2 + 2 cyclo-reversion of the cyclobutanone moiety and have been intercepted by benzyl alcohol and benzyl amine to form the corresponding benzyl esters and amides respectively.
{"title":"Photochemical generation of ketenes from phenanthrene-based cyclobutanones","authors":"Alexander D. Roth, Zhazira Koldasbay, Brett H. Ford, Khaidar Kairbek, Heejoon Ahn, Tarini S. Hardikar, Katherine M. Lane, Sarah M. Haynes, Dasan M. Thamattoor","doi":"10.1016/j.tet.2024.134344","DOIUrl":"10.1016/j.tet.2024.134344","url":null,"abstract":"<div><div>Various 9,10-cyclopropanated phenanthrenes have been shown previously to be viable photochemical precursors to many different types of carbenes. There is also one known example in the literature of a related approach used to generate diphenylketene from a phenanthrene-derived cyclobutanone in a laser flash photolysis study. In an effort to broaden the scope of this promising yet under-utilized method of ketene generation, the synthesis and characterization of several phenanthrene-based cyclobutanones, and their subsequent photolysis to produce a variety of ketenes, are presented in this report. The ketenes are produced, along with phenanthrene, by a formal 2 + 2 cyclo-reversion of the cyclobutanone moiety and have been intercepted by benzyl alcohol and benzyl amine to form the corresponding benzyl esters and amides respectively.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"168 ","pages":"Article 134344"},"PeriodicalIF":2.1,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142587330","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-29DOI: 10.1016/j.tet.2024.134347
D. Jérémy Liwara , Anton Pavlov , Jon E. Johansen , Pim E.G. Leonards , Sicco Brandsma , Jacob de Boer , Huiling Liu
Per- and polyfluoroalkyl substances (PFAS) have been widely studied due to their persistence in the environment and potential risks to wildlife and human health. The identification and analysis of these thousands of compounds in various environmental matrices is crucial for assessing their presence and evaluating potential risks. However, the growing list of suspected PFAS necessitates the synthesis of pure standards, for the development and validation of analytical methods. This study describes the synthesis of ten sulfonamide-based PFAS precursors suspected to be in the environment potentially because of the use of aqueous film forming foams (AFFFs). Starting materials, delivered as isomer mixtures were purified by recrystallization using a benzylamine intermediate as a protecting group. The targeted compounds were obtained by alkylation of this benzyl intermediate followed by a deprotection step using hydrogen and a palladium catalyst. This method was evaluated on different PFAS classes. The ten synthesized compounds, including N-dimethylamminopropyl perfluoroalkane sulfonamides (AmPr-FASA) and N-trimethylammoniopropyl perfluoroalkane sulfonamides (PFASAmS), N-sulfopropyl perfluorohexane sulfonamide (SPr-FHxSA), N-dimethylaminopropyl perfluorohexane sulfonamidopropylsulfate (AmPr-FHxSAPS), N-perfluorobutane sulfonamide (FBSA) and N-perfluorobutane sulfonamidoethanol (FBSE) were characterized by NMR and HRMS. These reference materials will be valuable for developing and validating analytical methods for emerging PFAS in environmental samples.
{"title":"Synthesis of reference standards for emerging sulfonamide PFAS precursors suspected in aqueous film-forming foams via a benzyl intermediate","authors":"D. Jérémy Liwara , Anton Pavlov , Jon E. Johansen , Pim E.G. Leonards , Sicco Brandsma , Jacob de Boer , Huiling Liu","doi":"10.1016/j.tet.2024.134347","DOIUrl":"10.1016/j.tet.2024.134347","url":null,"abstract":"<div><div>Per- and polyfluoroalkyl substances (PFAS) have been widely studied due to their persistence in the environment and potential risks to wildlife and human health. The identification and analysis of these thousands of compounds in various environmental matrices is crucial for assessing their presence and evaluating potential risks. However, the growing list of suspected PFAS necessitates the synthesis of pure standards, for the development and validation of analytical methods. This study describes the synthesis of ten sulfonamide-based PFAS precursors suspected to be in the environment potentially because of the use of aqueous film forming foams (AFFFs). Starting materials, delivered as isomer mixtures were purified by recrystallization using a benzylamine intermediate as a protecting group. The targeted compounds were obtained by alkylation of this benzyl intermediate followed by a deprotection step using hydrogen and a palladium catalyst. This method was evaluated on different PFAS classes. The ten synthesized compounds, including <em>N</em>-dimethylamminopropyl perfluoroalkane sulfonamides (AmPr-FASA) and <em>N</em>-trimethylammoniopropyl perfluoroalkane sulfonamides (PFASAmS), <em>N</em>-sulfopropyl perfluorohexane sulfonamide (SPr-FHxSA), <em>N</em>-dimethylaminopropyl perfluorohexane sulfonamidopropylsulfate (AmPr-FHxSAPS), <em>N</em>-perfluorobutane sulfonamide (FBSA) and <em>N</em>-perfluorobutane sulfonamidoethanol (FBSE) were characterized by NMR and HRMS. These reference materials will be valuable for developing and validating analytical methods for emerging PFAS in environmental samples.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"169 ","pages":"Article 134347"},"PeriodicalIF":2.1,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657409","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号