68965-44-6Relevant academic research and scientific papers
Synthesis of (benzenesulfonyl)difluoromethyl thioethers from ((difluoromethyl)sulfonyl)benzene and organothiocyanates generatedin situ
Dai, Jianjun,Shen, Xiao,Wu, Cheng,Xu, Huajian,Xu, Jun
supporting information, p. 7607 - 7610 (2021/09/22)
Easily available aryl and alkyl thiocyanates were converted into the corresponding (benzenesulfonyl)difluoromethyl thioethersviathe direct nucleophilic substitution of ((difluoromethyl)-sulfonyl)benzene under transition metal free conditions. Combined wit
Regio- and chemoselectivity in S- and O- difluoromethylation reactions using diethyl (bromodifluoromethyl)phosphonate
Amir, Dafna,Binyamin, Iris,Drug, Eyal,Fridkin, Gil,Gershonov, Eytan,Marciano, Daniele,Redy-Keisar, Orit,Yehezkel, Lea,Zafrani, Yossi
, (2021/09/08)
The effective difluoromethylations of various S- and O- based- nucleophiles, presenting a wide range of pKa values, using diethyl(bromodifluoromethyl) phosphonate (1) under basic conditions is described. These reactions, which rely on the quantitative generation of difluorocarbene formed through the hydrolysis of 1, were found to be effective only once the starting materials had pKa values of less than ca. 11. Importantly, in cases in which the substrates held two or three nucleophilic centers this feature was successfully implemented to achieve a high chemo- or regioselective difluoromethylation of the center exhibiting the lowest pKa value and the highest polarizability.
Iron-Catalyzed, Site-Selective Difluoromethylthiolation (-SCF2H) and Difluoromethylselenation (-SeCF2H) of Unactivated C(sp3)-H Bonds in N-Fluoroamides
Zhang, Hongwei,Yu, Fei,Li, Chuang,Tian, Peiyuan,Zhou, Yulu,Cao, Zhong-Yan
supporting information, p. 4721 - 4725 (2021/06/28)
The iron-catalyzed δ-C(sp3)-H bond difluoromethylthiolation and difluoromethylselenation of aliphatic amides with high site selectivity are reported. Essential to the success is the employment of an amide radical formed in situ to activate the inert C(sp3
Nickel-Catalyzed Decarbonylative Synthesis of Fluoroalkyl Thioethers
Brigham, Conor E.,Malapit, Christian A.,Lalloo, Naish,Sanford, Melanie S.
, p. 8315 - 8320 (2020/08/28)
This report describes the development of a nickel-catalyzed decarbonylative reaction for the synthesis of fluoroalkyl thioethers (RFSR) from the corresponding thioesters. Readily available, inexpensive, and stable fluoroalkyl carboxylic acids (RFCO2H) serve as the fluoroalkyl (RF) source in this transformation. Stoichiometric organometallic studies reveal that RF-S bond-forming reductive elimination is a challenging step in the catalytic cycle. This led to the identification of diphenylphosphinoferrocene as the optimal ligand for this transformation. Ultimately, this method was applied to the construction of diverse fluoroalkyl thioethers (RFSR), with R = both aryl and alkyl.
Asymmetric Difluoromethylthiolation of Carbon Nucleophiles with Optically Pure Difluoromethylthiolating Reagents Derived from Camphorsultam
Zhang, He,Wan, Xiaolong,Shen, Qilong
, p. 1041 - 1050 (2019/11/05)
The invention of a family of optically pure electrophilic difluoromethylthiolating reagents 9a–c based on the camphorsultam skeleton was described. These reagents reacted with a variety of soft carbon nucleophiles such as oxazolone, oxindole, benzolactone and β-ketoester in good to excellent enantioselectivities.
Preparation method for difluoromethyl-substituted sulfoaryl sulfonate
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Paragraph 0054-0058, (2018/04/01)
The invention discloses a preparation method for difluoromethyl-substituted sulfoaryl sulfonate. The preparation method comprises a step of subjecting a compound as show in a formula 2 which is described in the specification or a salt thereof and difluoro
Preparation method for N-difluoromethylthiophthalimide compound
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Paragraph 0070-0076, (2018/03/01)
The invention discloses a preparation method for a N-difluoromethylthiophthalimide compound. The preparation method comprises a step of subjecting difluoromethanesulfonyl chloride and a compound as show in a formula 1 which is described in the specification to difluoromethylthiolation in an organic solvent so as to obtain the N-difluoromethylthiophthalimide compound as show in a formula 3 which isdescribed in the specification. The preparation method of the invention has the advantages of simple operation, few steps, a wide scope of applicable substrates, mild reaction conditions, a high reaction conversion rate, high yield, low cost and suitability for industrial production.
Efficient Difluoromethylation of Alcohols Using TMSCF2Br as a Unique and Practical Difluorocarbene Reagent under Mild Conditions
Xie, Qiqiang,Ni, Chuanfa,Zhang, Rongyi,Li, Lingchun,Rong, Jian,Hu, Jinbo
supporting information, p. 3206 - 3210 (2017/03/17)
A general method for the efficient difluoromethylation of alcohols using commercially available TMSCF2Br (TMS=trimethylsilyl) as a unique and practical difluorocarbene source is developed. This method allows primary, secondary, and even tertiary alkyl difluoromethyl ethers to be synthesized under weakly basic or acidic conditions. The reaction mainly proceeds through the direct interaction between a neutral alcohol and difluorocarbene, which is different from the difluoromethylation of phenols. Moreover, alcohols containing other moieties that are also reactive toward difluorocarbene can be transformed divergently by using TMSCF2Br. This research not only solves the synthetic problem of difluorocarbene-mediated difluoromethylation of alcohols, it also provides new insights into the different reaction mechanisms of alcohol difluoromethylation and phenol difluoromethylation with difluorocarbene species.
A Two-Step, One-Pot, and Multigram-Scale Synthesis of N-Difluoromethylthiophthalimide
Zhu, Dianhu,Hong, Xin,Li, Dezhi,Lu, Long,Shen, Qilong
, p. 1383 - 1387 (2017/09/22)
A new method for the 100 g scale synthesis of N-difluoromethylthiophthalimide 1 from cheap commodity chemical benzyl mercaptan and HCF2Cl or other difluorocarbene precursors was described. Reagent 1 is an excellent electrophilic difluoromethylthiolating reagent as demonstrated by the gram-scale synthesis of five difluoromethylthiolated derivatives of structurally complicated drug-like molecules and natural products.
Radical Difluoromethylation of Thiols with (Difluoromethyl)triphenylphosphonium Bromide
Heine, Niklas B.,Studer, Armido
supporting information, p. 4150 - 4153 (2017/08/14)
A method for facile difluoromethylation of various thiols using (difluoromethyl)triphenylphosphonium bromide under mild reaction conditions is presented. The transformation proceeds in the absence of any transition metal using a bench-stable and readily accessible phosphonium salt. Deuterium labeling experiments and cyclic voltammetry measurements reveal that the difluoromethylation occurs via a SRN1-type mechanism. Substrate scope is broad, and various functional groups are tolerated (OH, NH2, amide, ester).
