- Reaction of Trimethylsilyl Azide with C=N-O Bond
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Trimethylsilyl azide (TMSA) was reacted with an oxime ester or a Reissert salt in the presence of trimethylsilyl trifluoromethanesulfonate to give tetrazole derivative.The details of these reactions are examined.
- Nishiyama, Kozaburo,Miyata, Izumi
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- N-Alkylation of N-trimethylsilyl derivatives of lactams, amides, and imides with alkyl sulfonates
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The reaction of N-trimethylsilyl derivatives of amides and imides with alkyl sulfonates on heating affords the corresponding N-alkyl derivatives and trimethylsilyl sulfonates.
- Baukov, Yu. I.,Kramarova, E. P.,Negrebetsky, Vad. V.,Shagina, A. D.,Shipov, A. G.,Tarasenko, D. V.
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- Synthesis of Benzylic Alcohols by C-H Oxidation
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Selective methylene C-H oxidation for the synthesis of alcohols with a broad scope and functional group tolerance is challenging due to the high proclivity for further oxidation of alcohols to ketones. Here, we report the selective synthesis of benzylic alcohols employing bis(methanesulfonyl) peroxide as an oxidant. We attempt to provide a rationale for the selectivity for monooxygenation, which is distinct from previous work; a proton-coupled electron transfer mechanism (PCET) may account for the difference in reactivity. We envision that our method will be useful for applications in the discovery of drugs and agrochemicals.
- Tanwar, Lalita,B?rgel, Jonas,Ritter, Tobias
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supporting information
p. 17983 - 17988
(2019/11/14)
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- Three hydrocarbyl silicon-based acrylate or three hydrocarbyl silicon-based methyl acrylate preparation method
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The invention relates to a preparation method of trialkyl-silicon-based acrylate or trialkyl-silicon-based methacrylate and belongs to the technical field of preparation of silane compounds. The preparation method comprises the following two steps: step one, reacting trialkyl silane alkoxide and oxygen-containing inorganic acid or sulfonic acid to generate silicon-based inorganic acid ester or silicon-based sulfonic acid ester; and step two, reacting silicon-based inorganic acid ester or silicon-based sulfonic acid ester and acrylate or methyl acrylate in the presence of a polymerization inhibitor, so as to obtain trialkyl-silicon-based acrylate or trialkyl-silicon-based methacrylate. Because only two reaction steps are adopted, and by utilizing the subsequent filtration and refining, the yield and purity are high, the requirement of industrial amplification production can be met; because no hydrogen chloride or hydrogen chloride salt is generated during the reactions, the corrosion effect on equipment is very light; by utilizing the trialkyl silane alkoxide rather than the trialkyl chlorosilane, the raw material polluting the environment is avoided.
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Paragraph 0029-0030
(2020/05/08)
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- Catalytic allylation of aldehydes with allyltrimethylsilane using in situ-generated trimethylsilyl methanesulfonate (TMSOMs) as a catalyst
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One-pot allylation reactions of carbonyl compounds with allyltrimethylsilane catalyzed by in situ-generated TMSOMs were carried out. TMSOMs was found to be an efficient catalyst in the allylation of the hydrates of α-keto aldehyde and glyoxylate. In situ-generated TMSOMs also can catalyze the SMS reaction of the aldehydes giving the functionalized homoallylic ethers in good to excellent yields.
- Wang, Ming Wen,Chen, Yong Jun,Wang, Dong
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p. 385 - 387
(2007/10/03)
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- Anhydrides of Phosphorus and Sulfur Acids, 2. Mixed Anhydrides of Phosphoric, Phosphonic, and Phosphinic Acids with Sulfonic Acids and Sulfuric Monoimidazolide. New Methods of Synthesis, Novel Structures, Phosphorylating Properties
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New applications of methods leading to anhydrides RR'P(O)OSO2R'' (1) are described: a) Reaction of acids RR'P(O)OH (2) with sulfonic imidazolides. b) Reaction of phosphorus imidazolides 4 with sulfonic acids and sulfonic anhydrides.New methods of synthesis of anhydrides 1 have been developed. c) Reaction of phosphorus acid silyl esters RR'P(O)OSiMe3 (9) with methanesulfonic and trifluoromethanesulfonic anhydrides. d) Reaction of bis(trimethylsilyl) tert-butylphosphonate (10) with methanesulfonic acid leading to tBuP(O)(OSO2Me)2 (11). e) Reaction of stannyl phosphate (EtO)2P(O)OSnMe3 (15) with methanesulfonic anhydride. f) Reaction of phosphorus acid silyl esters 9 with trimethylsilyl trifluoromethanesulfonate.All methods result in high yields and can be adapted to a variety of anhydrides 1 derived from phosphoric, phosphonic, and phosphinic acids on the one hand and methanesulfonic, trifluoromethanesulfonic acids and sulfuric monoimidazolide on the other.Phosphonium intermediates have been demonstrated by low temperature FT 31P NMR spectroscopy for reaction b) and c).The anhydrides 1 are readily converted into imidazolides 4 by the reaction with N-(trimethylsilyl)imidazole which proceeds via two distinct phosphonium intermediates.With neutral and weakly basic nucleophiles, the anhydrides 1 behave as phosphorylating agents.
- Dabkowski, Wojciech,Michalski, Jan,Skrzypczynski, Zbigniew
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p. 1809 - 1824
(2007/10/02)
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