Trifluoromethanesulfonyl azide as a bifunctional reagent for metal-free azidotrifluoromethylation of unactivated alkenes

Huang, Honggui; Li, Weishuang; Zhong, Dayou; Wang, Hu-Chong; Zhao, Jing; Liu, Wen‐Bo

doi:10.1039/d0sc06473d

Cited by 18 publications

(6 citation statements)

References 73 publications

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“…243 In 2021, this initiator was used in the reaction of azidotrifluoromethylation of unactivated alkenes 110.1 with triflyl azide 110.2 via radical chain mechanism by Liu and co-workers (Scheme 110). 244 The reaction proceeds at 80 °C in ethyl acetate and shows noticeably higher yields when using perfluorinated benzoyl peroxide compared to non-fluorinated benzoyl peroxide. Besides, perfluorobenzoyl peroxide has been used in aromatic oxygenation photoreaction.…”

Section: Polyfluoroarenes As Catalysts and Initiatorsmentioning

confidence: 99%

Radical reactions enabled by polyfluoroaryl fragments: photocatalysis and beyond

Zubkov,

Dilman

2024

Chem. Soc. Rev.

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Section: Polyfluoroarenes As Catalysts and Initiatorsmentioning

confidence: 99%

Radical reactions enabled by polyfluoroaryl fragments: photocatalysis and beyond

Zubkov,

Dilman

2024

Chem. Soc. Rev.

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“…Very recently, Liu and coworkers have employed trifluoromethanesulfonyl azide (CF 3 SO 2 N 3 ) in the azido‐trifluoromethylation of alkenes as a bifunctional reagent to simultaneously install both CF 3 and N 3 groups at the double bond (Scheme 90). [104] The above reagent can be readily prepared in situ by reacting trifluoromethanesulfonic anhydride with sodium azide in hexane but has never been used as both a CF 3 and N 3 source before. Perfluoro benzoyl peroxide was essential for initiating the radical chain reaction generating the CF 3 radical.…”

Section: Amino‐trifluoromethylationmentioning

confidence: 99%

Evolution and Future of Hetero‐ and Hydro‐Trifluoromethylations of Unsaturated C−C Bonds

et al. 2023

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The difunctionalizative trifluoromethylation of unsaturated CÀ C bonds is a highly useful and efficient method for the synthesis of trifluoromethyl compounds with attractive architectures from simple feedstocks, allowing the introduction of the CF 3 group along with a wide variety of substituents either inter-or intramolecularly. Given that trifluoromethyl molecules are increasingly used as promising bioactive species in the design of new drugs and agrochemicals, difunctionalizative trifluoromethylation has been extensively studied during the last decade. This review focuses on reactions proceeding via the simultaneous formation of CÀ heteroatom (O, N, S, Se, B) and CÀ H bonds, as these reactions provide useful CF 3 group-containing building blocks. To identify the trends and prospects of the evolution of this methodology, we systematically describe the variants of these types of reactions and provide a more general view of reaction conditions, modes, and mechanisms. The presented comprehensive survey enables the categorization of reactions into those that are synthetically mature and those with room for further development. 1.Shintaro Kawamura completed his Ph.D. at Kyoto University in 2013 under the supervision of Prof. Masaharu Nakamura. Since 2012, he has worked in Prof. Mikiko Sodeoka's group at RIKEN. He was promoted from a postdoctoral researcher to a Research Scientist (2017) and then to a Senior Research Scientist (2021) at RIK-EN. Dr. Kawamura's research interests include fluoroalkylation reactions based on the precise reactivity control of radical species. Pablo Barrio completed his Ph.D. at the University of Oviedo in 2007 under the supervision of Prof. Barluenga. After a postdoctoral role in the group of Prof. Carreira at ETH Zurich, he joined the group of Prof. Fustero in 2009 as a Juan de la Cierva Fellow, working for several years in the field of organofluorine chemistry. In 2018, he moved to Oviedo as a Ramón y Cajal Fellow, joining the Selective Organic Synthesis (SOS) group. Dr. Barrio's research interests include gold catalysis. Santos Fustero studied Chemistry at the University of Zaragoza, where he obtained his B.S. and Ph.D. under the supervision of Prof. Barluenga and Prof. Gotor. He spent two years as a postdoctoral research associate at Prof. Lehmkuhl's laboratory at Max-Planck-Institut für Kohlenforschung in Mülheim an der Ruhr, Germany. In 1983, he became Associate Professor at the University of Oviedo, Spain, and was promoted to Full Professor at the University of Valencia in 1990. In 2005, he became a research group leader at Centro de Investigación Príncipe Felipe in Valencia. Prof. Fustero's research interests include organofluorine and medicinal chemistry, organocatalysis, heterocyclic chemistry, and new reaction methodologies. Jorge Escorihuela received his Ph.D. in Chemistry at Universitat Jaume I (Castellon, Spain) in 2009. After a postdoctoral stage at Universitat Politècnica de València (UPV), he worked at Wageningen University and Research (the Netherlands) with Prof. Zuilho...

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“…To date, efficient methods for the access to vicinal trifluoromethyl azides from alkenes in a catalytic manner are limited. Following Renaud’s work, the trifluoromethanesulfonyl azide (CF 3 SO 2 N 3 , 140 - 7 ) was recently designed as a versatile reagent for the transfer of diazo and trifluoromethyl groups into alkenes in the presense of pentafluorobenzoyl peroxide (Scheme C) . Liu’s synthetic procedure was illustrated by a concise late-stage modification of drug and natural product derivatives, including Q-ACID, glucose, salicyclic acid, and l -tyrosine (Scheme D).…”

Section: Radical-mediated Desulfonylation Of N-containing Sulfonyl De...mentioning

confidence: 99%

“…reagent for the transfer of diazo and trifluoromethyl groups into alkenes in the presense of pentafluorobenzoyl peroxide (Scheme 140C). 513 Liu's synthetic procedure was illustrated by a concise late-stage modification of drug and natural product derivatives, including Q-ACID, glucose, salicyclic acid, and L-tyrosine (Scheme 140D). The radical initiator, peroxide, is thought to initiate the generation of the nascent trifluoromethanesulfonyl radical 140-13, and SO 2 extrusion forms the CF 3 radical 140-14 (Scheme 140E).…”

Section: Sulfonyl Azides As Azidated Reagentsmentioning

confidence: 99%

Desulfonylation via Radical Process: Recent Developments in Organic Synthesis

et al. 2021

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As the "chemical chameleon", sulfonyl-containing compounds and their variants have been merged with various types of reactions for the efficient construction of diverse molecular architectures by taking advantage of their incredible reactive flexibility. Currently, their involvement in radical transformations, in which the sulfonyl group typically acts as a leaving group via selective C−S, N−S, O−S, S−S, and Se−S bond cleavage/ functionalization, has facilitated new bond formation strategies which are complementary to classical two-electron cross-couplings via organometallic or ionic intermediates. Considering the great influence and synthetic potential of these novel avenues, we summarize recent advances in this rapidly expanding area by discussing the reaction designs, substrate scopes, mechanistic studies, and their limitations, outlining the state-of-the-art processes involved in radical-mediated desulfonylation and related transformations. With a specific emphasis on their synthetic applications, we believe this review will be useful for medicinal and synthetic organic chemists who are interested in radical chemistry and radical-mediated desulfonylation in particular. CONTENTS

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Trifluoromethanesulfonyl azide as a bifunctional reagent for metal-free azidotrifluoromethylation of unactivated alkenes

Abstract: A two-component and metal-free azidotrifluoromethylation of alkenes is realized using readily synthesized trifluoromethanesulfonyl azide (N3SO2CF3) as a bifunctional reagent for both CF3 and N3 groups.

Cited by 18 publications

References 73 publications

Radical reactions enabled by polyfluoroaryl fragments: photocatalysis and beyond

Radical reactions enabled by polyfluoroaryl fragments: photocatalysis and beyond

Evolution and Future of Hetero‐ and Hydro‐Trifluoromethylations of Unsaturated C−C Bonds

Desulfonylation via Radical Process: Recent Developments in Organic Synthesis

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