- Efficient synthesis of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate: A versatile precursor to o-benzyne
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(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.
- Bronner, Sarah M.,Garg, Neil K.
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- Improved synthesis of the benzyne precursor 2-(trimethylsilyl)phenyl trifluoromethanesulfonate
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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
- Atkinson, Darcy J.,Sperry, Jonathan,Brimble, Margaret A.
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- Expanding the Chemical Space of Succinate Dehydrogenase Inhibitors via the Carbon-Silicon Switch Strategy
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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.
- 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
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p. 3965 - 3971
(2021/05/04)
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- One-Pot Generation of Benzynes from Phenols: Formation of Primary Anilines by the Deoxyamination of Phenols
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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.
- Akai, Shuji,Ikawa, Takashi,Masuda, Shigeaki
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- Trifluoromethyl aryl sulfonates (TFMS): An applicable trifluoromethoxylation reagent
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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%).
- Lei, Meng,Miao, Hang,Wang, Xueyuan,Zhang, Wen,Zhu, Chengjian,Lu, Xiaqiang,Shen, Jian,Qin, Yanru,Zhang, Haoyang,Sha, Sijia,Zhu, Yongqiang
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supporting information
p. 1389 - 1392
(2019/04/30)
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- Access to Highly Functionalized Indanes from Arynes and α,γ-Diketo Esters
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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
- Hu, Wanyao,Zhang, Cong,Huang, Jie,Guo, Yingying,Fu, Zhenqian,Huang, Wei
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supporting information
p. 941 - 945
(2019/05/16)
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- Radical Truce-Smiles reactions on an isoxazole template: Scope and limitations
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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.
- Rashid, Srood O.,Almadhhi, Sultan S.,Berrisford, David J.,Raftery, James,Vitorica-Yrezabal, Inigo,Whitehead, George,Quayle, Peter
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p. 2413 - 2430
(2019/03/23)
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- 2-(Trimethylsilyl)phenyl Trimethylsilyl Ethers as Stable and Readily Accessible Benzyne Precursors
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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,
- Ikawa, Takashi,Masuda, Shigeaki,Nakajima, Hiroki,Akai, Shuji
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p. 4242 - 4253
(2017/04/27)
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- Alkyl substituted [2.2]paracyclophane-1,9-dienes
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[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.
- Lidster, Benjamin J.,Kumar, Dharam R.,Spring, Andrew M.,Yu, Chin-Yang,Helliwell, Madeleine,Raftery, James,Turner, Michael L.
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p. 6079 - 6087
(2016/07/06)
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- Development and Application of O-(Trimethylsilyl)aryl Fluorosulfates for the Synthesis of Arynes
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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
- Chen, Qiao,Yu, Hongmei,Xu, Zhaoqing,Lin, Li,Jiang, Xianxing,Wang, Rui
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p. 6890 - 6896
(2015/10/06)
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- Continuous-flow synthesis of trimethylsilylphenyl perfluorosulfonate benzyne precursors
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2-(Trimethylsilyl)phenyl perfluorosulfonated aryne precursors may now be accessed using flow chemistry, enabling the fast preparation of pure compounds with no requirement for low temperature lithiation or column chromatography. The process has been adapted to novel nonaflate precursors, utilizing the cheaper and more user-friendly nonaflyl fluoride reagent. The resultant nonaflates are shown to successfully participate in a range of aryne reaction classes.
- Michel, Boris,Greaney, Michael F.
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supporting information
p. 2684 - 2687
(2014/06/09)
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- Novel one-pot synthesis of xanthones via sequential fluoride ion-promoted fries-type rearrangement and nucleophilic aromatic substitution
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A novel and efficient synthesis of xanthones is described. 2-(Trimethylsilyl)phenyl 2-fluorobenzoate derivatives undergo Fries-type rearrangement and intramolecular SNAr reaction in a one-pot sequential manner under fluoride ion-promoted mild conditions. The method provides efficient access to xanthones that have significant steric congestion around the C9 carbonyl, which are not readily available by conventional methods. Georg Thieme Verlag Stuttgart · New York.
- Fujimoto, Yuuki,Itakura, Ryohei,Hoshi, Hiroki,Yanai, Hikaru,Ando, Yoshio,Suzuki, Keisuke,Matsumoto, Takashi
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supporting information
p. 2575 - 2580
(2013/12/04)
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- A domino process for benzyne preparation: Dual activation of o-(trimethylsilyl)phenols by nonafluorobutanesulfonyl fluoride
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Benzynes were generated from o-(trimethylsilyl)phenols using nonafluorobutanesulfonyl fluoride (NfF) by a domino process, i.e., the nonaflation of the phenolic hydroxyl group of o-(trimethylsilyl)phenols by NfF followed by the attack of the produced fluoride ion on the trimethylsilyl group. The generated benzyne immediately underwent various reactions to give polysubstituted benzenes.
- Ikawa, Takashi,Nishiyama, Tsuyoshi,Nosaki, Toshifumi,Takagi, Akira,Akai, Shuji
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supporting information; experimental part
p. 1730 - 1733
(2011/06/16)
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- Development of Odorless Thiols and Sulfides and Their Applications to Organic Synthesis
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Development of new odorless thiols (dodecanethiol, 4-n- heptylphenylmethanethiol, 4-trimethylsilylphenylmethanethiol, 4-trimethylsilylbenzenethiol) and an odorless sulfide (1-methylsulfanyldodecane) and their applications to dealkylation, Michael addition, Swern oxidation, and Corey-Kim oxidation are described.
- Nishide, Kiyoharu,Ohsugi, Shin-Ichi,Miyamoto, Tetsuo,Kumar, Kamal,Node, Manabu
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p. 189 - 200
(2007/10/03)
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- Synthetic equivalents of benzenethiol and benzyl mercaptan having faint smell: Odor reducing effect of trialkylsilyl group
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Syntheses and odor tests of the trialkylsilylated benzyl mercaptans and benzenethiols have revealed that the trimethylsilyl substituent on the benzene ring has a remarkable effect in reducing the foul smell of the parent benzyl mercaptan and benzenethiol.
- Nishide, Kiyoharu,Miyamoto, Tetsuo,Kumar, Kamal,Ohsugi, Shin-Ichi,Node, Manabu
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p. 8569 - 8573
(2007/10/03)
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- Synthesis of biaryls by intramolecular radical aryl migration from silicon to carbon
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(equation presented) A new method for the preparation of biaryls via intramolecular 1,5 aryl migration reaction from silicon in silyl ethers to aryl radicals is presented. Various readily available diphenylsilyl ethers can be used as substrates in this reaction. Functionalized aryl groups can also be transferred. The analogous 1,4 aryl migration reaction is less efficient.
- Studer, Armido,Bossart, Martin,Vasella, Tomaso
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p. 985 - 988
(2007/10/03)
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- N-cumyl benzamide, sulfonamide, and aryl O-carbamate directed metalation groups. Mild hydrolytic lability for facile manipulation of directed ortho metalation derived aromatics
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(Matrix Presented) N-Cumyl benzamide (2), sulfonamide (8), and O-carbamate (11) compounds undergo directed ortho metalation under standard conditions to give, after quench with a variety of electrophiles, the substituted products 3, 9, and 12, respectively. Regiospecific and convenient approaches to phthalimides (7), 1,2-benzisothiazole 1,1-dioxides (10b), and ortho-substituted phenols (13a) and salicylamides (13b) are thereby established The mild deprotection protocol for these new cumyl directed metalation groups (DMGs) suggests that they will supersede previous corresponding groups for synthetic anionic aromatic chemistry.
- Metallinos, Costa,Nerdinger, Sven,Snieckus, Victor
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p. 1183 - 1186
(2008/02/09)
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- Photographic silver halide material and process
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Photographic silver halide materials and processes employ at least one coupler having a coupling-off group which includes a carbocyclic or heterocyclic ring which bears a silyl substituent on at least one of its ring carbon atoms and is attached via another of its ring atoms either directly or through a linking group or atom to the coupling position of the coupler. The silyl substituent bears three groups which are independently aromatic groups, heterocyclic groups, aliphatic groups, carbocyclic groups or additional silyl groups bonded through a linking atom to the silicon atom in said silyl substituent.
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- Method of preparation of organosilyl substituted aromatic or heteroaromatic compounds
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An improved method of preparing an ortho-, meta- or para-silyl aromatic or heteroaromatic compound represented by the formula STR1 wherein X is oxygen or sulfur, R1 represents the atoms necessary to complete an unsubstituted or substituted arom
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- ORTHO LITHIATION DIRECTED BY AMINO GROUPS ON SILICON IN PHENYLSILANE DERIVATIVES
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Phenylsilanes, which contain trimethylethylenediamino (Me2NCH2CH2NMe-) group(s) on silicon, undergo selective ortho lithiation by treatment with t-BuLi, providing a new method for the synthesis of ortho substituted phenylsilane derivatives.
- Tamao, Kohei,Yao, Hajime,Tsutsumi, Yasushi,Abe, Hideyuki,Hayashi, Takashi,Ito, Yoshihiko
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p. 2925 - 2928
(2007/10/02)
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- Methylenecyclopropanes IX. - Methylenecyclopentanes by Metal-Catalyzed Cycloaddition of 1-Methylene-2-(trimethylsilyl)cyclopropane with Electron-Deficient Olefins
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Monocyclic cyclopentanes such as 2a-c as well as certain bicyclic derivatives are prepared in high yields by cycloadditions of 1-methylene-2-(trimethylsilyl)cyclopropane (1) with electron-deficient olefins catalyzed by triisopropylphosphane containing palladium(0) compounds.The trimethylsilyl group can be easily displaced by protolysis with trifluoroacetic acid yielding the methylenecyclopentanes 6a-c or 9a and 10a.Therefore, 1 can be regarded as a synthetic equivalent of methylenecyclopropane.
- Binger, Paul,Sternberg, Ethan,Wittig, Ute
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p. 1933 - 1938
(2007/10/02)
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- Process for preparing polyisocyanato/polyisocyanurates by catalytic cyclotrimerization of polyisocyanates
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Polyisocyanurate/polyisocyanates of enhanced stability are prepared by partial catalytic cyclotrimerization of a polyisocyanate in the presence of a catalytically effective amount of an aminosilyl catalyst and wherein the cyclotrimerization reaction is terminated when a predetermined desired amount of isocyanurate groups has been attained, by adding to the reaction mixture, after the cooling thereof to a temperature of below 50° C., a reaction terminating amount of an organic catalyst deactivating compound comprising at least one free hydroxyl moiety, or the reaction product of such hydroxylated organic catalyst deactivating compound with an isocyanate.
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- Aromatization of Arene 1,2-Oxides. 1-(Trimethylsilyl)benzene 1,2-Oxide
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Aromatization of 1-(trimethylsilyl)benzene 1,2-oxide (1) affords a mixture of o-(trimethylsilyl)phenol and phenol, the ratio of which is pH dependent.Aromatization of -1-(trimethylsilyl)benzene 1,2-oxide gave the following results. (1) At pH 1.1 or 7 all the deuterium label in o-(trimethylsilyl)phenol was para to the hydroxyl group. (2) At pH 1.1 the phenol formed was exclusively phenol, but at pH 7 it was 70-75percent phenol and 25-30percent phenol.The pathway of the aromatization reaction is discussed.
- Epp, James E. Van,Boyd, Derek R.,Berchtold, Glenn A.
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p. 1817 - 1820
(2007/10/02)
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