- Dehydrogenative Silylation of Alcohols Under Pd-Nanoparticle Catalysis
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Pd-nanoparticle-catalyzed dehydrogenative coupling between various hydrosilanes and alcohols was shown to provide silyl ethers in good and reproducible yields. The synthetic methodology is effective for a wide range of simple and bulky silanes and secondary alcohols, while keeping various other functional groups intact. The procedure also exhibits high selectivity for the silylation of primary versus secondary alcohols in 1,2-diols, and allows the successive silylation of alkynols and hydrogenation of the triple bond to afford Z-alkenols in good yields.
- Pramanik, Suman,Fernandes, Anthony,Liautard, Virginie,Pucheault, Mathieu,Robert, Frederic,Landais, Yannick
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supporting information
p. 728 - 732
(2019/01/04)
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- Amine-free silylation of alcohols under 4-methylpyridine N-oxide-catalyzed conditions
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Amine-free silylation of various alcohols catalyzed by 4-methylpyridine N-oxide in the presence of MS4A at room temperature was developed. This simple method gave various silyl ethers in a high yield.
- Yoshida, Keisuke,Fujino, Yuta,Itatsu, Yukihiro,Inoue, Hiroki,Kanoko, Yohei,Takao, Ken-Ichi
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p. 627 - 631
(2016/01/20)
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- Hydromethylation of Unactivated Olefins
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A solution to the classic unsolved problem of olefin hydromethylation is presented. This highly chemoselective method can tolerate labile and reactive chemical functionalities and uses a simple set of reagents. An array of olefins, including mono-, di-, and trisubstituted olefins, are all smoothly hydromethylated. This mild protocol can be used to simplify the synthesis of a specific target or to directly "edit" complex natural products and other advanced materials. The method is also amenable to the simple installation of radioactive and stable labeled methyl groups.
- Dao, Hai T.,Li, Chao,Michaudel, Quentin,Maxwell, Brad D.,Baran, Phil S.
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supporting information
p. 8046 - 8049
(2015/07/15)
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- Silyl methallylsulfinates: Efficient and powerful agents for the chemoselective silylation of alcohols, polyols, phenols and carboxylic acids
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Alcohols, phenols and carboxylic acids are silylated with very good yields in the presence of silyl methallylsulfinates under non-basic conditions and with the formation of volatile co-products. The Royal Society of Chemistry 2005.
- Huang, Xiaogen,Craita, Cotinica,Awad, Loay,Vogel, Pierre
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p. 1297 - 1299
(2008/03/28)
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- Solvent-modulated Pd/C-catalyzed deprotection of silyl ethers and chemoselective hydrogenation
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Recently we have reported undesirable and frequent deprotection of the TBDMS protective group of a variety of hydroxyl functions occurred under neutral and mild hydrogenation conditions using 10% Pd/C in MeOH. The deprotection of silyl ethers is susceptible to significant solvent effect. TBDMS and TES protecting groups were selectively cleaved in the presence of acid-sensitive functional groups such as TIPS ether, TBDPS ether and dimethyl acetal under hydrogenation condition using 10% Pd/C in MeOH. In contrast, chemoselective hydrogenation of reducible functional groups such as acetylene, olefin and benzyl ether, proceeds in the presence of TBDMS or TES ethers in AcOEt or MeCN.
- Ikawa, Takashi,Hattori, Kazuyuki,Sajiki, Hironao,Hirota, Kosaku
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p. 6901 - 6911
(2007/10/03)
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- Allyl, methallyl, prenyl, and methylprenyl ethers as protected alcohols: Their selective cleavage with diphenyldisulfone under neutral conditions
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Diphenyldisulfone is a mild and efficient reagent for selective cleavage of methylprenyl (2,3-dimethylbut-2-en-1-yl), prenyl (3-methylbut-2-en1-yl), and methallyl (2-methylallyl) ethers. These reaction conditions are compatible with the presence of other protecting groups such as acetals, acetates, and allyl, benzyl, and TBDMS ethers. Exposure of 2,3-dimethylbut-2-en-1-yl and 3-methylbut-2-en1-yl ethers to diphenyldisulfone led to the formation of 2,3-dimethylbuta-1,3-diene and isoprene, respectively. 2-Methylallyl ethers undergo isomerization to 2-methylpropenyl ethers, which are easily hydrolyzed into the corresponding free alcohols and isobutyraldehyde.
- Markovic, Dean,Vogel, Pierre
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p. 2693 - 2696
(2007/10/03)
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- Preparation of formate esters from O-TBDMS/O-TES protected alcohols. A one-step conversion using the Vilsmeier-Haack complex POCl3/DMF
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O-tert-Butyldimethylsilylated (O-TBDMS) or O-triethylsilylated (O-TES) alcohols were converted in one step to their corresponding formates under Vilsmeier-Haack conditions (POCl3/DMF). The scope and limitations of this novel reaction for interconverting alcohol protecting groups are described.
- Koeller, Sylvain,Lellouche, Jean-Paul
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p. 7043 - 7046
(2007/10/03)
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- Silyl Halides from (Phenylseleno)silanes. Reaction with Oxiranes and Alcohols To Give Hydrolytically Stable Silyl Ethers.
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The preparation of (phenylseleno)silanes and their reactions with halogens (Cl2, Br2, I2) to give silyl halides and diphenyl diselenide are described.Highly hindered tert-butyldimethyl and tert-butyl diphenylsilyl halides were easily prepared.The reaction of silyl bromides and iodides with oxiranes followed by diazabicyclononane treatment gave allylic alcohol silyl ethers.Tertiary alcohols reacted rapidly with silyliodides to give hydrolytically stable silyl ethers.Treatment of the silyl ethers with tetra-n-butylammonium fluoride gave the free alcohols withoutrearrangement or isomerization.
- Detty, Michael R.,Seidler, Mark D.
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p. 1283 - 1292
(2007/10/02)
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