15288-53-6Relevant academic research and scientific papers
Efficient synthesis of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate: A versatile precursor to o-benzyne
Bronner, Sarah M.,Garg, Neil K.
, p. 8842 - 8843 (2009)
(Chemical Equation Presented) An efficient procedure for the gram-scale preparation of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate, a versatile precursor to o-benzyne, is presented. The three-step sequence utilizes phenol as the starting material, requires only one chromatographic purification, and ultimately delivers the desired silyltriflate in 66% overall yield. 2009 American Chemical Society.
Improved synthesis of the benzyne precursor 2-(trimethylsilyl)phenyl trifluoromethanesulfonate
Atkinson, Darcy J.,Sperry, Jonathan,Brimble, Margaret A.
, p. 911 - 913 (2010)
An alternate procedure for the preparation of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate, a coveted benzyne precursor, is described. Modifications to existing methods result in a dramatic reduction in the overall reaction time and eliminate the us
Expanding the Chemical Space of Succinate Dehydrogenase Inhibitors via the Carbon-Silicon Switch Strategy
Wei, Ge,Huang, Ming-Wei,Wang, Wen-Jie,Wu, Yuan,Mei, Shu-Fen,Zhou, Li-Ming,Mei, Long-Can,Zhu, Xiao-Lei,Yang, Guang-Fu
, p. 3965 - 3971 (2021/05/04)
The carbon-silicon switch strategy has become a key technique for structural optimization of drugs to widen the chemical space, increase drug activity against targeted proteins, and generate novel and patentable lead compounds. Flubeneteram, targeting succinate dehydrogenase (SDH), is a promising fungicide candidate recently developed in China. We describe the synthesis of novel SDH inhibitors with enhanced fungicidal activity to enlarge the chemical space of flubeneteram by employing the C-Si switch strategy. Several of the thus formed flubeneteram-silyl derivatives exhibited improved fungicidal activity against porcine SDH compared with the lead compound flubeneteram and the positive controls. Disease control experiments conducted in a greenhouse showed that trimethyl-silyl-substituted compound W2 showed comparable and even higher fungicidal activities compared to benzovindiflupyr and flubeneteram, respectively, even with a low concentration of 0.19 mg/L for soybean rust control. Furthermore, compound W2 encouragingly performed slightly better control than azoxystrobin and was less active than benzovindiflupyr at the concentration of 100 mg/L against soybean rust in field trials. The computational results showed that the silyl-substituted phenyl moiety in W2 could form strong van der Waals (VDW) interactions with SDH. Our results indicate that the C-Si switch strategy is an effective method for the development of novel SDH inhibitors.
One-Pot Generation of Benzynes from Phenols: Formation of Primary Anilines by the Deoxyamination of Phenols
Akai, Shuji,Ikawa, Takashi,Masuda, Shigeaki
, (2020/03/23)
Benzynes were selectively generated in situ from phenols and trapped regioselectively with potassium hexamethyldisilazide to form primary anilines following acidic workup. The direct conversion of a phenolic hydroxyl group into a free amino group is a useful method for the preparation of primary aryl amines that are hard to synthesize by using coupling reactions involving phenol derivatives with ammonia. Whereas reactions of ortho- and meta-substituted phenols produced meta-substituted anilines exclusively, those of para-substituted phenols provided ortho-silylanilines.
Radical Truce-Smiles reactions on an isoxazole template: Scope and limitations
Rashid, Srood O.,Almadhhi, Sultan S.,Berrisford, David J.,Raftery, James,Vitorica-Yrezabal, Inigo,Whitehead, George,Quayle, Peter
, p. 2413 - 2430 (2019/03/23)
The use of TiCl3-HCl as promotor in the radical Truce-Smiles reactions of 2-(((3,5-dimethylisoxazol-4-yl)sulfonyl)oxy)benzenediazonium salts has been investigated in detail. During these reactions the desired Truce-Smiles rearrangement (via an ipso-substitution reaction) is accompanied by the formation of a number of by-products including dihydrobenzo[5,6][1,2]oxathiino[3,4-d]isoxazole 4,4-dioxides, dioxidobenzo[e][1,2]oxathiin-3-yl)ethan-1-ones, anilines and chloroaromatics. Replacing TiCl3-HCl by Cu(NO3)2-Cu2O as reductant in these reactions was found to afford broadly comparable product distributions. Competition and radical clock experiments also provide an indication of the relative susceptibility of the isoxazole nucleus towards attack by aryl radicals.
Trifluoromethyl aryl sulfonates (TFMS): An applicable trifluoromethoxylation reagent
Lei, Meng,Miao, Hang,Wang, Xueyuan,Zhang, Wen,Zhu, Chengjian,Lu, Xiaqiang,Shen, Jian,Qin, Yanru,Zhang, Haoyang,Sha, Sijia,Zhu, Yongqiang
supporting information, p. 1389 - 1392 (2019/04/30)
Fluorine is probably another favorite hetero-atom for incorporation into small molecules after nitrogen. Among many fluorine-containing groups, trifluoromethyl aryl ethers (ArOCF3) have unique properties in drug design and are difficult to be synthesized, and many different methods were developed to prepare them. A novel one-pot synthesis of o-iodine-aryl trifluoromethyl ethers (ArOCF3I) was described by the reaction of trifluoromethoxylation and iodination with trifluoromethyl aryl sulfonates (TFMS) in this manuscript. The reaction conditions were optimized by screening different solvents, crown ethers, substrates and the ratios and the yields of products were in moderate to high yields (up to 86%).
Access to Highly Functionalized Indanes from Arynes and α,γ-Diketo Esters
Hu, Wanyao,Zhang, Cong,Huang, Jie,Guo, Yingying,Fu, Zhenqian,Huang, Wei
supporting information, p. 941 - 945 (2019/05/16)
An unprecedented method for the synthesis of highly functionalized indanes from arynes and α,γ-diketo esters is described. Importantly, mild and nearly pH-neutral conditions ensure excellent functional group tolerance. Theoretical studies indicated that t
2-(Trimethylsilyl)phenyl Trimethylsilyl Ethers as Stable and Readily Accessible Benzyne Precursors
Ikawa, Takashi,Masuda, Shigeaki,Nakajima, Hiroki,Akai, Shuji
, p. 4242 - 4253 (2017/04/27)
Stable 2-(trimethylsilyl)phenyl trimethylsilyl ethers, readily obtained from the corresponding halogenated phenols in two steps, were identified as novel benzyne precursors. These species were converted to benzynes by a domino reaction of O-desilylation,
Alkyl substituted [2.2]paracyclophane-1,9-dienes
Lidster, Benjamin J.,Kumar, Dharam R.,Spring, Andrew M.,Yu, Chin-Yang,Helliwell, Madeleine,Raftery, James,Turner, Michael L.
, p. 6079 - 6087 (2016/07/06)
[2.2]Paracyclophane-1,9-dienes substituted with n-octyl chains have been synthesised from the corresponding dithia[3.3]paracyclophanes using a benzyne induced Stevens rearrangement. The use of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate and tetra-n-butylammonium fluoride as the in situ benzyne source gave significantly improved yields over traditional sources of benzyne and enabled the preparation of n-octyl substituted [2.2]paracyclophane-1,9-dienes on a multi-gram scale.
Development and Application of O-(Trimethylsilyl)aryl Fluorosulfates for the Synthesis of Arynes
Chen, Qiao,Yu, Hongmei,Xu, Zhaoqing,Lin, Li,Jiang, Xianxing,Wang, Rui
, p. 6890 - 6896 (2015/10/06)
A class of o-(trimethylsilyl)aryl fluorosulfates was synthesized by a concise method and successfully used as aryne precursors for the first time. Different trapping agents such as azides, furans, and acyl acetoacetates could successfully react with the a
