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Trifluoromethylthiolation and Trifluoromethylselenolation of α‐Diazo Esters Catalyzed by Copper 下载免费PDF全文
Christian Matheis Prof. Dr. Lukas J. Goossen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(35):12270-12273
α‐Diazo esters are smoothly converted into the corresponding trifluoromethyl thio‐ or selenoethers by reaction with Me4NSCF3 or Me4NSeCF3, respectively, in the presence of catalytic amounts of copper thiocyanate. This straightforward method gives high yields under neutral conditions at room temperature and is applicable to a wide range of functionalized molecules, including diverse α‐amino acid derivatives. It is well‐suited for the late‐stage introduction of trifluoromethylthio or ‐seleno groups into drug‐like molecules. 相似文献
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《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(1):175-178
Upon activation under superacid conditions, functionalized tailor‐made N‐SCF3 sulfenamides served as reagents for the trifluoromethylthiolation of aromatic amines. This method has a broad substrate scope and can be used for the late‐stage functionalization of complex molecules such as alkaloids or steroids. Mechanistic studies based on in situ low‐temperature NMR spectroscopy revealed the involvement of dicationic superelectrophilic intermediates. 相似文献
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Synthesis of Difluoromethyl Thioethers from Difluoromethyl Trimethylsilane and Organothiocyanates Generated In Situ 下载免费PDF全文
Bilguun Bayarmagnai Christian Matheis Dr. Kévin Jouvin Prof. Dr. Lukas J. Goossen 《Angewandte Chemie (International ed. in English)》2015,54(19):5753-5756
A copper‐CF2H complex generated in situ from copper thiocyanate and TMS? CF2H smoothly converts organothiocyanates into valuable difluoromethyl thioethers. This reaction step can be combined with several thiocyanation methods to one‐pot protocols, allowing late‐stage difluoromethylthiolations of widely available alkyl halides and arenediazonium salts. This strategy enables the introduction of difluoromethylthio groups—a largely unexplored substituent with highly promising properties—into drug‐like molecules. 相似文献
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Sophie I. Arlow Prof. John F. Hartwig 《Angewandte Chemie (International ed. in English)》2016,55(14):4567-4572
A copper‐catalyzed coupling of aryl, heteroaryl, and vinyl iodides with α‐silyldifluoroamides is reported. The reaction forms α,α‐difluoro‐α‐aryl amides from electron‐rich, electron‐poor, and sterically hindered aryl iodides in high yield and tolerates a variety of functional groups. The aryldifluoroamide products can be transformed further to provide access to a diverse array of difluoroalkylarenes, including compounds of potential biological interest. 相似文献
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Rapid and Efficient Copper‐Catalyzed Finkelstein Reaction of (Hetero)Aromatics under Continuous‐Flow Conditions 下载免费PDF全文
Dr. Mao Chen Saki Ichikawa Prof. Dr. Stephen L. Buchwald 《Angewandte Chemie (International ed. in English)》2015,54(1):263-266
A general, rapid, and efficient method for the copper‐catalyzed Finkelstein reaction of (hetero)aromatics has been developed using continuous flow to generate a variety of aryl iodides. The described method can tolerate a broad spectrum of functional groups, including N‐H and O‐H groups. Additionally, in lieu of isolation, the aryl iodide solutions were used in two distinct multistep continuous‐flow processes (amidation and Mg–I exchange/nucleophilic addition) to demonstrate the flexibility of this method. 相似文献
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A Copper(I)‐Catalyzed Enantioselective γ‐Boryl Substitution of Trifluoromethyl‐Substituted Alkenes: Synthesis of Enantioenriched γ,γ‐gem‐Difluoroallylboronates 下载免费PDF全文
Dr. Ryoto Kojima Sota Akiyama Prof. Dr. Hajime Ito 《Angewandte Chemie (International ed. in English)》2018,57(24):7196-7199
The first catalytic enantioselective γ‐boryl substitution of CF3‐substituted alkenes is reported. A series of CF3‐substituted alkenes was treated with a diboron reagent in the presence of a copper(I)/Josiphos catalyst to afford the corresponding optically active γ,γ‐gem‐difluoroallylboronates in high enantioselectivity. The thus obtained products could be readily converted into the corresponding difluoromethylene‐containing homoallylic alcohols using highly stereospecific allylation reactions. 相似文献
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Direct Access to α,α‐Difluoroacylated Arenes by Palladium‐Catalyzed Carbonylation of (Hetero)Aryl Boronic Acid Derivatives 下载免费PDF全文
Thomas L. Andersen Mette W. Frederiksen Katrine Domino Prof. Dr. Troels Skrydstrup 《Angewandte Chemie (International ed. in English)》2016,55(35):10396-10400
A palladium‐catalyzed carbonylative coupling of (hetero)aryl boronates or boronic acid salts with carbon monoxide and α‐bromo‐α,α‐difluoroamides and bromo‐α,α‐difluoroesters is described herein. The method is useful for the synthesis of a diverse selection of (hetero)aryl α,α‐difluoro‐β‐ketoamides and α,α‐difluoro‐β‐ketoesters, which are useful building blocks for the generation of functionalized difluoroacylated and difluoroalkyl arenes. The method could be further extended to a one‐pot protocol for the formation of difluoroacetophenones. 相似文献
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Synthesis of Aryl Tri‐ and Difluoromethyl Thioethers via a CH‐Thiocyanation/Fluoroalkylation Cascade 下载免费PDF全文
Dr. Kévin Jouvin Christian Matheis Prof. Dr. Lukas J. Goossen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(41):14324-14327
An AlCl3‐catalyzed C?H thiocyanation was discovered and combined with a Langlois‐type trifluoromethylation to afford aryl trifluoromethyl thioethers directly from arenes, N‐thiocyanatosuccinimide (NTS) and Ruppert–Prakash reagent. An analogous combination with a copper‐mediated difluoromethylation gives access to aryl difluoromethyl thioethers. Both processes proceed with exceptional regioselectivity for the most electron‐rich, sterically least hindered position of the arene. The sulfur and fluoroalkyl groups originate from different sources, so that the use of expensive, preformed fluoroalkylthiolation reagents is avoided. 相似文献
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Direct Trifluoromethylthiolation and Perfluoroalkylthiolation of C(sp2)H Bonds with CF3SO2Na and RfSO2Na 下载免费PDF全文
Lvqi Jiang Jinlong Qian Prof. Dr. Wenbin Yi Guoping Lu Chun Cai Prof. Dr. Wei Zhang 《Angewandte Chemie (International ed. in English)》2015,54(49):14965-14969
A new method for CF3SO2Na‐based direct trifluoromethylthiolation of C(sp2)? H bonds has been developed. CF3SSCF3 is generated in situ from cheap and easy‐to‐handle CF3SO2Na, and in the presence of CuCl can be used for electrophilic trifluoromethylthiolation of indoles, pyrroles, and enamines. The method has been extended to perfluoroalkylthiolation reactions using RfSO2Na. 相似文献
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Qian Wang Chuanfa Ni Mingyou Hu Qiqiang Xie Qinghe Liu Shitao Pan Jinbo Hu 《Angewandte Chemie (International ed. in English)》2020,59(22):8507-8511
A Cu‐catalyzed gem‐bis(trifluoromethyl)olefination of α‐diazo esters, using TMSCF3 as the only fluorocarbon source, has been developed and provides an exquisite method to access gem‐bis(trifluoromethyl)alkenes. This unprecedented olefination process involves a carbene migratory insertion into “CuCF3” to generate the α‐CF3‐substituted organocopper species, which then undergoes β‐fluoride elimination and two consecutive addition‐elimination processes to give the desired products. The key to this efficient one‐pot C1‐to‐C3 synthetic protocol lies in the controllable double (over single and triple) trifluoromethylations of the gem‐difluoroalkene intermediates. 相似文献
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Copper‐Catalyzed Intermolecular Trifluoromethylazidation of Alkenes: Convenient Access to CF3‐Containing Alkyl Azides 下载免费PDF全文
Fei Wang Xiaoxu Qi Zhaoli Liang Dr. Pinhong Chen Prof. Dr. Guosheng Liu 《Angewandte Chemie (International ed. in English)》2014,53(7):1881-1886
A novel copper‐catalyzed intermolecular trifluoromethylazidation of alkenes has been developed under mild reaction conditions. A variety of CF3‐containing organoazides were directly synthesized from a wide range of olefins, including activated and unactivated alkenes, and the resulting products can be easily transformed into the corresponding CF3‐containing amine derivatives. 相似文献
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Direct Catalytic Trifluoromethylthiolation of Boronic Acids and Alkynes Employing Electrophilic Shelf‐Stable N‐(trifluoromethylthio)phthalimide 下载免费PDF全文
M. Sc. Roman Pluta M. Sc. Pavlo Nikolaienko Prof. Dr. Magnus Rueping 《Angewandte Chemie (International ed. in English)》2014,53(6):1650-1653
A new and safe method for the synthesis of N‐(trifluoromethylthio)phthalimide, a convenient and shelf‐stable reagent for the direct trifluoromethylthiolation, has been developed. N‐(Trifluoromethylthio)phthalimide can be used as an electrophilic source of F3CS+ and reacts readily with boronic acids and alkynes under copper catalysis. The utility of CF3S‐containing molecules as biologically active agents, the mild reaction conditions employed, and the high tolerance of functional groups demonstrate the potential of this new methodology to be widely applied in organic synthesis as well as industrial pharmaceutical and agrochemical research and development. 相似文献
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Ji‐Wei Gu Qiao‐Qiao Min Ling‐Chao Yu Prof. Dr. Xingang Zhang 《Angewandte Chemie (International ed. in English)》2016,55(40):12270-12274
A nickel‐catalyzed three‐component reaction for the synthesis of difluoroalkylated compounds through tandem difluoroalkylation‐arylation of enamides has been developed. The reaction tolerates a variety of arylboronic acids and widely available difluoroalkyl bromides, and even the relatively inert substrate chlorodifluoroacetate. The significant advantages of this protocol are the low‐cost nickel catalyst, synthetic convenience, excellent functional‐group compatibility and high reaction efficiency. 相似文献
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Copper‐Catalyzed Reaction of Trifluoromethylketones with Aldehydes via a Copper Difluoroenolate 下载免费PDF全文
Ryohei Doi Prof. Dr. Masato Ohashi Prof. Dr. Sensuke Ogoshi 《Angewandte Chemie (International ed. in English)》2016,55(1):341-344
A copper‐catalyzed reaction of easily accessible α,α,α‐trifluoromethylketones with various aldehydes affords difluoro‐methylene compounds in the presence of diboron and NaOtBu. The key process of the reaction is the formation of a copper difluoroenolate by 1,2‐addition of a borylcopper intermediate to α,α,α‐trifluoromethylketones and subsequent β‐fluoride elimination. Mechanistic studies including the isolation and characterization of a possible anionic copper alkoxide intermediate are also described. 相似文献