{"title":"高价碘化物(III)介导的硫脲类/硫代氨基甲酰氟与水和亲核氟化源的烯烃和炔烃硫氟化反应","authors":"Junyi Zhou, Xiang Wang, Wenjun Tang, Liqin Jiang","doi":"10.1039/d4qo01569j","DOIUrl":null,"url":null,"abstract":"Hypervalent iodines(III) mediated oxo/aza/carbon/difluorination of alkenes have made significant progress although the corresponding fluorination of alkynes cannot been accomplished. However, hypervalent iodine(III) mediated thiofluorination of both alkenes and alkynes has never been achieved before. Herein, three-component alkenyl thiocarbamoyl fluorides, water, and Et3N·3HF or two-component alkenyl thioureas and Et3N·3HF proceeded through cascade hydrolysis/thiofluorination or thiofluorination of terminal/internal unactivated/activated alkenes upon phenyliodine(III)bis(pivalate) in tolune at room temperature, providing access to diversified monofluorinated 1,3-thiazolidin-2-ones, 1,3-thiazinan-2-ones, 2-imino-thiazolidines and 1,3-thiazinan-2-imines with broad substrate scope, excellent functional group tolerance and excellent regioselectivity. Configurations of some products were found to be opposite to those expected from traditional mechanism of activation olefin by hypervalent iodines(III). Based on mechanistic study and product configurations, another mechanism involving cyclic sulfonium ion intermediate was proposed. This inspired us to further discover that phenyliodine(III)bis(pivalate) with dioxane as solvent enabled thiofuorination of alkynes from alkynyl thioureas and Et3N·3HF, furnishing 2-imino-thiazolidines bearing an exocyclicfluoromethylene as tetrasubstituted fluorinated alkenes with remarkable regio-, chemo- and stereoselectivity (absolute E-isomer). These transformations represent unprecedented thiofluorination of alkenes/alkynes in one operation directly from nucleophilic sulfur reagents and nucleophilic fluorine reagent.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":4.6000,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Hypervalent Iodide(III)-Mediated Thiofluorination of Alkenes and Alkynes from Thioureas/Thiocarbamoyl Fluorides with Water and Nucleophilic Fluoride Source\",\"authors\":\"Junyi Zhou, Xiang Wang, Wenjun Tang, Liqin Jiang\",\"doi\":\"10.1039/d4qo01569j\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Hypervalent iodines(III) mediated oxo/aza/carbon/difluorination of alkenes have made significant progress although the corresponding fluorination of alkynes cannot been accomplished. However, hypervalent iodine(III) mediated thiofluorination of both alkenes and alkynes has never been achieved before. Herein, three-component alkenyl thiocarbamoyl fluorides, water, and Et3N·3HF or two-component alkenyl thioureas and Et3N·3HF proceeded through cascade hydrolysis/thiofluorination or thiofluorination of terminal/internal unactivated/activated alkenes upon phenyliodine(III)bis(pivalate) in tolune at room temperature, providing access to diversified monofluorinated 1,3-thiazolidin-2-ones, 1,3-thiazinan-2-ones, 2-imino-thiazolidines and 1,3-thiazinan-2-imines with broad substrate scope, excellent functional group tolerance and excellent regioselectivity. Configurations of some products were found to be opposite to those expected from traditional mechanism of activation olefin by hypervalent iodines(III). Based on mechanistic study and product configurations, another mechanism involving cyclic sulfonium ion intermediate was proposed. This inspired us to further discover that phenyliodine(III)bis(pivalate) with dioxane as solvent enabled thiofuorination of alkynes from alkynyl thioureas and Et3N·3HF, furnishing 2-imino-thiazolidines bearing an exocyclicfluoromethylene as tetrasubstituted fluorinated alkenes with remarkable regio-, chemo- and stereoselectivity (absolute E-isomer). These transformations represent unprecedented thiofluorination of alkenes/alkynes in one operation directly from nucleophilic sulfur reagents and nucleophilic fluorine reagent.\",\"PeriodicalId\":97,\"journal\":{\"name\":\"Organic Chemistry Frontiers\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.6000,\"publicationDate\":\"2024-10-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organic Chemistry Frontiers\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d4qo01569j\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, ORGANIC\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic Chemistry Frontiers","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4qo01569j","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
Hypervalent Iodide(III)-Mediated Thiofluorination of Alkenes and Alkynes from Thioureas/Thiocarbamoyl Fluorides with Water and Nucleophilic Fluoride Source
Hypervalent iodines(III) mediated oxo/aza/carbon/difluorination of alkenes have made significant progress although the corresponding fluorination of alkynes cannot been accomplished. However, hypervalent iodine(III) mediated thiofluorination of both alkenes and alkynes has never been achieved before. Herein, three-component alkenyl thiocarbamoyl fluorides, water, and Et3N·3HF or two-component alkenyl thioureas and Et3N·3HF proceeded through cascade hydrolysis/thiofluorination or thiofluorination of terminal/internal unactivated/activated alkenes upon phenyliodine(III)bis(pivalate) in tolune at room temperature, providing access to diversified monofluorinated 1,3-thiazolidin-2-ones, 1,3-thiazinan-2-ones, 2-imino-thiazolidines and 1,3-thiazinan-2-imines with broad substrate scope, excellent functional group tolerance and excellent regioselectivity. Configurations of some products were found to be opposite to those expected from traditional mechanism of activation olefin by hypervalent iodines(III). Based on mechanistic study and product configurations, another mechanism involving cyclic sulfonium ion intermediate was proposed. This inspired us to further discover that phenyliodine(III)bis(pivalate) with dioxane as solvent enabled thiofuorination of alkynes from alkynyl thioureas and Et3N·3HF, furnishing 2-imino-thiazolidines bearing an exocyclicfluoromethylene as tetrasubstituted fluorinated alkenes with remarkable regio-, chemo- and stereoselectivity (absolute E-isomer). These transformations represent unprecedented thiofluorination of alkenes/alkynes in one operation directly from nucleophilic sulfur reagents and nucleophilic fluorine reagent.
期刊介绍:
Organic Chemistry Frontiers is an esteemed journal that publishes high-quality research across the field of organic chemistry. It places a significant emphasis on studies that contribute substantially to the field by introducing new or significantly improved protocols and methodologies. The journal covers a wide array of topics which include, but are not limited to, organic synthesis, the development of synthetic methodologies, catalysis, natural products, functional organic materials, supramolecular and macromolecular chemistry, as well as physical and computational organic chemistry.