Haoran Li, Minyao Kuang, Yuwei Liu, Wei Yi, Shengdong Wang
Environmentally benign calcium(II) triflimide has emerged as a sustainable substitute for transition-metal catalysts, rare-earth metals, and strong Brønsted acids in promoting organic synthesis, thereby attracting considerable attention. Recently, elegant methodologies involving calcium(II) triflimide have been developed, such as cyclizations, dehydrative functionalizations, hydroarylation reactions, hydrofunctionalizations, reductions, rearrangements, and novel selenylations, hese have been applied to a diverse range of substrates inculding alcohols, alkenes, alkynes, carbonyl compounds, imines, N,O-acetals, and selenides for the formation of C–C or C–X bond. This review provides a comprehensive and detailed overview of the recent progress in the application of calcium(II) triflimideas as an organic synthesis catalyst, summarizing the crucial achievements in reaction methodologies and the plausible reaction mechanisms.
{"title":"Recent advances of calcium(II) triflimide in organic synthesis","authors":"Haoran Li, Minyao Kuang, Yuwei Liu, Wei Yi, Shengdong Wang","doi":"10.1039/d4qo02164a","DOIUrl":"https://doi.org/10.1039/d4qo02164a","url":null,"abstract":"Environmentally benign calcium(II) triflimide has emerged as a sustainable substitute for transition-metal catalysts, rare-earth metals, and strong Brønsted acids in promoting organic synthesis, thereby attracting considerable attention. Recently, elegant methodologies involving calcium(II) triflimide have been developed, such as cyclizations, dehydrative functionalizations, hydroarylation reactions, hydrofunctionalizations, reductions, rearrangements, and novel selenylations, hese have been applied to a diverse range of substrates inculding alcohols, alkenes, alkynes, carbonyl compounds, imines, N,O-acetals, and selenides for the formation of C–C or C–X bond. This review provides a comprehensive and detailed overview of the recent progress in the application of calcium(II) triflimideas as an organic synthesis catalyst, summarizing the crucial achievements in reaction methodologies and the plausible reaction mechanisms.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"11 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832170","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}
Tomaz Chorro, Clemens Kaussler, Julia V. Kolodiazhnaia, Frank Jensen, Troels Skrydstrup, Carlos Roque Correia
We report herein a novel, efficient, and expeditious approach for enantioselective intramolecular carbonylative Heck-Matsuda reaction, employing highly accessible, stable, and cost-effective nitroarenes as masked electrophiles. This tandem process combines the one-pot reduction of nitroarenes to the respective anilines, diazotization, Heck-Matsuda, carbonylation, and cyclization, enabling the synthesis of enantioenriched spirolactones. The method achieves overall yields of up to 76% with excellent enantiomeric ratios of up to 96:4 under mild conditions. Isotopically labeled products are readily obtained with near stoichiometric 13C carbon monoxide. Importantly, nitroarenes are used as masked electrophiles, which serve as an advantageous alternative to anilines and aryldiazonium salts for the Heck-Matsuda reaction. This approach thereby avoids the isolation of sensitive aryldiazonium salt intermediates and, consequently, the dangers associated with them. Density Functional Theory (DFT) calculations provide precise insights into the enantioenrichment mechanism, highlighting the significance of Pd carbonyl complexes for efficient diastereoconvergence. Microkinetic modeling of the computationally obtained reaction network results in an enantioenrichment of sub-kcal-accuracy in comparison to the experiment. This work not only showcases the level of complexity achievable in the field of tandem reactions but also highlights the utility of nitroarenes in complex organic transformations, demonstrating their potential for both academic and industrial applications.
{"title":"Tandem Synthesis of Enantioenriched Spirolactones via One-Pot Heck-Matsuda Reactions Directly from Nitroarenes","authors":"Tomaz Chorro, Clemens Kaussler, Julia V. Kolodiazhnaia, Frank Jensen, Troels Skrydstrup, Carlos Roque Correia","doi":"10.1039/d4qo01979b","DOIUrl":"https://doi.org/10.1039/d4qo01979b","url":null,"abstract":"We report herein a novel, efficient, and expeditious approach for enantioselective intramolecular carbonylative Heck-Matsuda reaction, employing highly accessible, stable, and cost-effective nitroarenes as masked electrophiles. This tandem process combines the one-pot reduction of nitroarenes to the respective anilines, diazotization, Heck-Matsuda, carbonylation, and cyclization, enabling the synthesis of enantioenriched spirolactones. The method achieves overall yields of up to 76% with excellent enantiomeric ratios of up to 96:4 under mild conditions. Isotopically labeled products are readily obtained with near stoichiometric 13C carbon monoxide. Importantly, nitroarenes are used as masked electrophiles, which serve as an advantageous alternative to anilines and aryldiazonium salts for the Heck-Matsuda reaction. This approach thereby avoids the isolation of sensitive aryldiazonium salt intermediates and, consequently, the dangers associated with them. Density Functional Theory (DFT) calculations provide precise insights into the enantioenrichment mechanism, highlighting the significance of Pd carbonyl complexes for efficient diastereoconvergence. Microkinetic modeling of the computationally obtained reaction network results in an enantioenrichment of sub-kcal-accuracy in comparison to the experiment. This work not only showcases the level of complexity achievable in the field of tandem reactions but also highlights the utility of nitroarenes in complex organic transformations, demonstrating their potential for both academic and industrial applications.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"23 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832217","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}
Trifluoromethylated heterocycles with a C−CF3 stereogenic center are prevalent scaffolds in many bioactive small molecules and pharmaceutical and agrochemical libraries. However, efficient methods for the construction of 2-trifluoromethyl-1-pyrroline scaffolds have remained elusive. Here we report the first rhodium-catalyzed three-component reaction of α-trifluoromethyl-N-triftosylhydrazones with nitriles and alkenes, providing rapid access to 2-trifluoromethyl-1-pyrrolines with a quaternary stereocenter from readily available starting materials. This method features mild reaction conditions, good functional group tolerance, high yields, and excellent diastereoselectivity. The synthetic utility has been further demonstrated by late-stage diversification of five complex bioactive molecules, scale-up reactions, and diverse post-synthetic transformations, yielding valuable trifluoromethylated pyrrolidine and pyrroline scaffolds. DFT calculation elucidates the origins of chemo- and diastereoselectivity and the mechanism that proceeds via the key nitrile ylide intermediate.
{"title":"Rhodium-Catalyzed [3 + 2] Cycloaddition of in situ Generated Nitrile Ylides with Alkenes: A Route to Quaternary 2-Trifluoromethyl-1-Pyrrolines","authors":"Caicai He, Linxuan Li, Shuang Li, Hongzhu Chen, Hongru Zhang, Yong Wu, Xiaolong Zhang, Paramasivam Sivaguru, Karunanidhi Murali, Xihe Bi","doi":"10.1039/d4qo01986e","DOIUrl":"https://doi.org/10.1039/d4qo01986e","url":null,"abstract":"Trifluoromethylated heterocycles with a C−CF3 stereogenic center are prevalent scaffolds in many bioactive small molecules and pharmaceutical and agrochemical libraries. However, efficient methods for the construction of 2-trifluoromethyl-1-pyrroline scaffolds have remained elusive. Here we report the first rhodium-catalyzed three-component reaction of α-trifluoromethyl-N-triftosylhydrazones with nitriles and alkenes, providing rapid access to 2-trifluoromethyl-1-pyrrolines with a quaternary stereocenter from readily available starting materials. This method features mild reaction conditions, good functional group tolerance, high yields, and excellent diastereoselectivity. The synthetic utility has been further demonstrated by late-stage diversification of five complex bioactive molecules, scale-up reactions, and diverse post-synthetic transformations, yielding valuable trifluoromethylated pyrrolidine and pyrroline scaffolds. DFT calculation elucidates the origins of chemo- and diastereoselectivity and the mechanism that proceeds via the key nitrile ylide intermediate.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"253 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832218","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}
Xu Yuan, Tong Zhou, Qiaoqiao Wang, Yu Chen, Xiaohong Cheng, Yi Jin
Herein, we report an Ag-catalyzed and difluorocarbene-promoted amide-ylide rearrangement strategy. This strategy utilizes an unconventional transformation between difluorocarbene and amide functionalities to successfully synthesize 3-salicyloylpyridines. Preliminary mechanistic studies suggest that the reaction initially involves the coordination of the amide with the metal, followed by a reaction with difluorocarbene to form the RNCF2H intermediate, which then facilitates the formation of the N-ylide intermediate, a crucial step for the synthesis of the target compound. Subsequently, selective C–N bond cleavage is followed by a rearrangement and elimination of formaldehyde. This rearrangement strategy demonstrates broad substrate applicability. Under identical reaction conditions, it enables the reaction of chromones with various β-ketones (such as 1,3-dicarbonyl compounds, β-keto esters, acetophenone, acetone, pentanone, and 2-Bromoacetophenone) to produce 3-salicyloylpyridines (>47 examples, up to 91% yield), showing excellent efficiency and functional group tolerance.
{"title":"Ag-Catalyzed and Difluorocarbene-Promoted Amide-Ylide Rearrangement: Synthesis of 3-Salicyloylpyridines","authors":"Xu Yuan, Tong Zhou, Qiaoqiao Wang, Yu Chen, Xiaohong Cheng, Yi Jin","doi":"10.1039/d4qo01961j","DOIUrl":"https://doi.org/10.1039/d4qo01961j","url":null,"abstract":"Herein, we report an Ag-catalyzed and difluorocarbene-promoted amide-ylide rearrangement strategy. This strategy utilizes an unconventional transformation between difluorocarbene and amide functionalities to successfully synthesize 3-salicyloylpyridines. Preliminary mechanistic studies suggest that the reaction initially involves the coordination of the amide with the metal, followed by a reaction with difluorocarbene to form the RNCF2H intermediate, which then facilitates the formation of the N-ylide intermediate, a crucial step for the synthesis of the target compound. Subsequently, selective C–N bond cleavage is followed by a rearrangement and elimination of formaldehyde. This rearrangement strategy demonstrates broad substrate applicability. Under identical reaction conditions, it enables the reaction of chromones with various β-ketones (such as 1,3-dicarbonyl compounds, β-keto esters, acetophenone, acetone, pentanone, and 2-Bromoacetophenone) to produce 3-salicyloylpyridines (>47 examples, up to 91% yield), showing excellent efficiency and functional group tolerance.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"18 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832172","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}
Yue Xia, Aaron D. Charlack, Rui Guo, Nicholas W. Wade, Yiming Wang
The hydrofluorination of enynes has been developed for the synthesis of fluorinated dienes. Using a pyridinium tetrafluoroborate salt that is easily prepared on large scale, this approach enabled the direct conversion of enynes to fluorinated diene targets through a vinyl cation mediated process. This approach was applied to a range of aryl-substituted enyne esters to deliver the (Z)-configured products with high levels of stereo- and regioselectivity. Mechanistic studies were conducted to provide insights into the stereochemical outcome and reaction efficiency under different reaction conditions.
{"title":"Access to Fluorinated Dienes through Hydrofluorination of 2-En-4-ynoates","authors":"Yue Xia, Aaron D. Charlack, Rui Guo, Nicholas W. Wade, Yiming Wang","doi":"10.1039/d4qo02049a","DOIUrl":"https://doi.org/10.1039/d4qo02049a","url":null,"abstract":"The hydrofluorination of enynes has been developed for the synthesis of fluorinated dienes. Using a pyridinium tetrafluoroborate salt that is easily prepared on large scale, this approach enabled the direct conversion of enynes to fluorinated diene targets through a vinyl cation mediated process. This approach was applied to a range of aryl-substituted enyne esters to deliver the (Z)-configured products with high levels of stereo- and regioselectivity. Mechanistic studies were conducted to provide insights into the stereochemical outcome and reaction efficiency under different reaction conditions.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"21 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841640","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}
Satenik Mkrtchyan, Vishal B. Purohit, Oleksandr Shalimov, Michał Jakubczyk, Gabriela Addová, Juraj Filo, Barbora Benicka, Ronak V. Prajapati, Vaibhav D. Prajapati, Jiří Zapletal, Yevhen Karpun, Vitaliy Yepishev, Jarmila Kmeťová, Elena Kupcová, Viktor Iaroshenko
A novel strategy has been introduced for the selective activation of N–C(O) moiety in primary aromatic amides through the utilization of pyrylium tetrafluoroborate under mechanochemical conditions, where the amide group undergoes subsequent activation and selectively substituted with the CF3 or OCF3 functionality. The scope of the present protocol includes selective transformation of diversely substituted aromatic amides to the respective trifluoromethyl and trifluoromethoxy arenes via mechanochemically induced deaminative functionalization under the synergy of a piezoelectric material barium titanate (BaTiO3), and ruthenium-catalysis. The presented mechanochemical approach unlocks new chemical spaces in pharmaceutical industries with a perspective on PASE (pot, atom, and step economy) synthesis.
{"title":"Mechanochemical Decarbonylative Transformation of Amide Group to OCF3 and CF3 Functionalities under Ruthenium Catalysis","authors":"Satenik Mkrtchyan, Vishal B. Purohit, Oleksandr Shalimov, Michał Jakubczyk, Gabriela Addová, Juraj Filo, Barbora Benicka, Ronak V. Prajapati, Vaibhav D. Prajapati, Jiří Zapletal, Yevhen Karpun, Vitaliy Yepishev, Jarmila Kmeťová, Elena Kupcová, Viktor Iaroshenko","doi":"10.1039/d4qo01946f","DOIUrl":"https://doi.org/10.1039/d4qo01946f","url":null,"abstract":"A novel strategy has been introduced for the selective activation of N–C(O) moiety in primary aromatic amides through the utilization of pyrylium tetrafluoroborate under mechanochemical conditions, where the amide group undergoes subsequent activation and selectively substituted with the CF3 or OCF3 functionality. The scope of the present protocol includes selective transformation of diversely substituted aromatic amides to the respective trifluoromethyl and trifluoromethoxy arenes via mechanochemically induced deaminative functionalization under the synergy of a piezoelectric material barium titanate (BaTiO3), and ruthenium-catalysis. The presented mechanochemical approach unlocks new chemical spaces in pharmaceutical industries with a perspective on PASE (pot, atom, and step economy) synthesis.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"24 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142820724","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}
β-Oxygen-containing sulfones are versatile building blocks in pharmaceuticals and chemical industry. Despite notable advancements in reportedmethods, a sustainable and general catalytic method for the preparation of β-oxygen-containing sulfones remains elusive due to the inherent reactivity disparities and notorious metal-catalyst-poisoning capability of sulfur nucleophiles. Here, we present a distinct multifunctional hexatungstate catalytic strategy for the synthesis of β-hydroxy sulfones and β‑keto sulfones through a sequential hydroxysulfenylation of alkenes/selective oxidation process, utilizing a commerically available thiol and green hydrogen peroxide as the ‘oxy-sulfonylation reagent’. This method not only offers a practical route for delivering functionalized sulfones from readily available chemicals but also showcases its versatility through late-stage oxysulfonylation of complex substrates and concise syntheses of bioactive molecules. Moreover, this modular methodology features hydroperoxide reductant free, mild reaction conditions, water as the sole byproduct and new mechanism.
{"title":"Modular Synthesis of β-Oxygen-containing Sulfones from Alkenes through Hexatungstate-catalyzed Cascade Hydroxysulfenylation/ Selective Oxidation","authors":"Xianghua Zeng, Jiaoxiong Li, Zhibin Zhou, Yongge Wei","doi":"10.1039/d4qo02151g","DOIUrl":"https://doi.org/10.1039/d4qo02151g","url":null,"abstract":"β-Oxygen-containing sulfones are versatile building blocks in pharmaceuticals and chemical industry. Despite notable advancements in reportedmethods, a sustainable and general catalytic method for the preparation of β-oxygen-containing sulfones remains elusive due to the inherent reactivity disparities and notorious metal-catalyst-poisoning capability of sulfur nucleophiles. Here, we present a distinct multifunctional hexatungstate catalytic strategy for the synthesis of β-hydroxy sulfones and β‑keto sulfones through a sequential hydroxysulfenylation of alkenes/selective oxidation process, utilizing a commerically available thiol and green hydrogen peroxide as the ‘oxy-sulfonylation reagent’. This method not only offers a practical route for delivering functionalized sulfones from readily available chemicals but also showcases its versatility through late-stage oxysulfonylation of complex substrates and concise syntheses of bioactive molecules. Moreover, this modular methodology features hydroperoxide reductant free, mild reaction conditions, water as the sole byproduct and new mechanism.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"22 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142820723","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}
We have developed a desymmetrization of 2,5-cyclohexadienones tethered 3-cyano-4-styrylcoumarins via the amino-squaramide catalyzed initial regio-/enantio-selective sulfa-1,6-addition to the 3-cyano-4-styrylcoumarin moiety of the substrate, followed by an intramolecular vinylogous 1,4-addition to the dienone portion. An additional sulfa-Michael addition was observed when the thiols were taken in excess to create an additional stereogenic center. With our divergent approach, the two unique classes of hydrophenanthrene skeletons have been synthesized as single diastereoisomers in good to excellent yields and enantioselectivities (up to >99.5:0.5 er).
{"title":"Stereocontrolled desymmetrization of 2,5-cyclohexadienones via organocatalytic domino sulfa-1,6-/1,4-addition or sulfa-1,6- /1,4-/sulfa-1,4-addition reactions","authors":"Vanisha Sodhi, Deepak Sharma, Manisha Sharma, Pankaj Chauhan","doi":"10.1039/d4qo02097a","DOIUrl":"https://doi.org/10.1039/d4qo02097a","url":null,"abstract":"We have developed a desymmetrization of 2,5-cyclohexadienones tethered 3-cyano-4-styrylcoumarins via the amino-squaramide catalyzed initial regio-/enantio-selective sulfa-1,6-addition to the 3-cyano-4-styrylcoumarin moiety of the substrate, followed by an intramolecular vinylogous 1,4-addition to the dienone portion. An additional sulfa-Michael addition was observed when the thiols were taken in excess to create an additional stereogenic center. With our divergent approach, the two unique classes of hydrophenanthrene skeletons have been synthesized as single diastereoisomers in good to excellent yields and enantioselectivities (up to >99.5:0.5 er).","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"336 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142823300","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}
Dearomatizationof pyridines is a robust synthetic method to access aza-heterocycles. Simultaneously, intermolecular cyclizative rearrangement is a recently developed new strategy toward efficiently constructing tetrasubstituted carbons. Here, we show that an effective integration of dearomatization approach with strategic cyclizative rearrangement render 2-acyl-substituted pyridines and their analogues with common isocyanates to undergo a tandem [3+2] heteroannulation followed by an extensive 1,2-carbon shift, thus providing a straightforward access to readily functionalized bicyclohydantoins. Based on the promotion of organophosphorus, different types of migrating groups, such as ester, amide, aryl and trifluoromethyl groups, are all well-tolerated in the same reaction for the first time.
{"title":"Cyclizative Dearomative Rearrangement of Pyridines with Isocyanates","authors":"Xing-Zi Li, Fang-Zhou Li, Zi-Qi Wang, Hua Wu","doi":"10.1039/d4qo02111h","DOIUrl":"https://doi.org/10.1039/d4qo02111h","url":null,"abstract":"Dearomatizationof pyridines is a robust synthetic method to access aza-heterocycles. Simultaneously, intermolecular cyclizative rearrangement is a recently developed new strategy toward efficiently constructing tetrasubstituted carbons. Here, we show that an effective integration of dearomatization approach with strategic cyclizative rearrangement render 2-acyl-substituted pyridines and their analogues with common isocyanates to undergo a tandem [3+2] heteroannulation followed by an extensive 1,2-carbon shift, thus providing a straightforward access to readily functionalized bicyclohydantoins. Based on the promotion of organophosphorus, different types of migrating groups, such as ester, amide, aryl and trifluoromethyl groups, are all well-tolerated in the same reaction for the first time.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142820721","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}
A chemo and regio-selective system for activating C=O and S=O bonds under transition metal-free conditions is described. Thus, a Tf2O-mediated 1,3-transposition of ynones in DMF has been developed, providing a versatile pathway for the downstream synthesis of diverse five- and seven-membered heterocycles. Furthermore, the catalytic migration of carbonyl functionality conjugated to an alkyne unit is investigated. In the presence of sulfoxide, which undergoes a Pummerer reaction, the in-situ generation of highly reactive sulfonium salts enables efficient access to a wide range of sulfur-containing annulated scaffolds. Importantly, 3-SCF2D chromones were obtained in high yields and D-incorporation. This divergent methodology offers a versatile platform for maximizing molecular complexity and diversity.
{"title":"Tf2O-Induced Selective 1,3-Transposition/Cyclization of Ynones in DMF","authors":"Huilin Lan, Wenting Liu, Wen Liu, Jiajian Peng, Ying Bai, Xinxin Shao","doi":"10.1039/d4qo01890g","DOIUrl":"https://doi.org/10.1039/d4qo01890g","url":null,"abstract":"A chemo and regio-selective system for activating C=O and S=O bonds under transition metal-free conditions is described. Thus, a Tf2O-mediated 1,3-transposition of ynones in DMF has been developed, providing a versatile pathway for the downstream synthesis of diverse five- and seven-membered heterocycles. Furthermore, the catalytic migration of carbonyl functionality conjugated to an alkyne unit is investigated. In the presence of sulfoxide, which undergoes a Pummerer reaction, the in-situ generation of highly reactive sulfonium salts enables efficient access to a wide range of sulfur-containing annulated scaffolds. Importantly, 3-SCF2D chromones were obtained in high yields and D-incorporation. This divergent methodology offers a versatile platform for maximizing molecular complexity and diversity.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"10 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142820722","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}
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