- Regio- And Stereoselective Hydroiodination of Internal Alkynes with Ex Situ-Generated HI
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Herein, we report an efficient and practical hydroiodination of internal alkynes using HI generated ex situ from the readily available triethylsilane and I2. This system offers high regio- and stereoselectivity to afford (E)-vinyl iodides in good yields under mild conditions. Furthermore, the hydroiodination reaction shows high functional group tolerance toward alkyl, methoxy, halogen, trifluoromethyl, cyano, ester, halomethyl, acid-sensitive silyl ether, and acetal moieties.
- Nozawa-Kumada, Kanako,Noguchi, Koto,Akada, Tomoya,Shigeno, Masanori,Kondo, Yoshinori
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supporting information
p. 6659 - 6663
(2021/09/08)
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- Iridium-catalyzed reduction of alkyl halides by triethylsilane
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A highly active cationic Ir(III) hydride complex catalyzes the reduction of primary, secondary, and tertiary chlorides, bromides, and iodides as well as certain fluorides by Et3SiH. The catalytic cycle appears to operate by a unique process in which an electrophilic iridium silane complex acts as a silylating reagent to produce a silyl-substituted halonium ion which is then readily reduced by the nucleophilic dihydride formed following silyl transfer. Copyright
- Yang, Jian,Brookhart, Maurice
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p. 12656 - 12657
(2008/03/14)
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- Acyl iodides in organic synthesis: IX. Cleavage of the Si-O-C and Si-O-Si moieties
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Reactions of acyl iodides RCOI (R = Me, Ph) with organosilicon compounds involve cleavage of the Si-O-C and Si-O-Si fragments. Acetyl iodide reacts with alkyl(alkoxy)silanes with evolution of heat, and cleavage of the Si-O bond results in the formation of oligo-or polysiloxanes, alkyl iodides, and alkyl acetates. 1,3-Diacetoxytetramethyldisiloxane is formed in the reaction of acetyl iodide with dimethoxy(dimethyl)silane. Acyl iodides readily react with 1-ethoxysilatrane to give 1-acyloxysilatranes as a result of cleavage of the C-O bond. The reaction of acetyl iodide with hexaethyldisiloxane yields triethylsilyl acetate and triethyliodosilane, while in the reaction with octamethyltrisiloxane iodo(trimethyl)silane and dimethyl(trimethylsiloxy)silyl acetate are obtained. Nauka/Interperiodica 2007.
- Voronkov,Trukhina,Belousova,Kuznetsova,Vlasova
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p. 501 - 506
(2008/02/02)
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- Acyl iodides in organic synthesis: X. Reactions with triorganylsilanes and triphenylgermane
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Reaction of acyl iodides RCOI (R = Me, Ph) with triorganylsilanes R′2R″SiH in toluene gives 50-60% of the corresponding triorganyliodosilanes R′2R″SiI. Triethylsilane reacts with the same acyl iodides under solvent-free conditions to afford the corresponding aldehyde and triethyliodosilane as primary products. Triethyliodosilane undergoes subsequent transformations into hexaethyldisiloxane and triethyl(acyloxy)silane Et3SiOCOR (R = Me, Ph). Reactions of acyl iodides RCOI (R = Me, Ph) with triphenylgermane in the absence of a solvent lead to formation of iodo(triphenyl)germane in more than 90% yield.
- Voronkov,Trukhina,Belousova,Tsyrendorzhieva,Vlasova
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experimental part
p. 1751 - 1753
(2009/09/29)
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- Process for the preparation of tetrahydrothieno [3,2-C] pyridine derivatives
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A process for the preparation of tetrahydrothieno[3,2-c]pyridine compound of formula 6: or their pharmaceutically acceptable salts, wherein the meaning of X is carboxyl, alkoxycarbonyl, aryloxycarbonyl, or carbamoyl of formula wherein R1 and R2 can be individually or simultaneously hydrogen, alkyl or part of a heterocyclic structure; Z can be hydrogen, halogen, alkyl, aryl, aryloxy or alkoxy group, the process comprising conducting a dehydroxylation reaction on the compound of formula 5 in order to obtain a compound of formula 6, wherein said dehydroxylation reaction is effected by iodosilane represented by the formula Si(R3)3I, wherein R3 selected from an alkyl, alkenyl, alkynyl, aromatic group, or combinations of thereof.
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Page/Page column 3
(2008/06/13)
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- Selective synthesis of halosilanes from hydrosilanes and utilization for organic synthesis
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Selective synthesis of halosilanes has been examined. Various types of halosilanes and halohydrosilanes, such as R3SiX, R2SiHX, R2SiX2, RSiH2X, RSiHX2 (X=Cl, Br, F), were obtained by the reactions of the corresponding hydrosilanes with Cu(II)-based reagents selectively in high yields. This method could be also applied to the synthesis of chlorofluorosilanes and chlorohydrogermanes. On the other hand, iodo- and bromosilanes and germanes were obtained by Pd- or Ni-catalyzed hydride-halogen exchange reactions of hydrosilanes with alkyl or allyl halides. Their synthetic applications have been demonstrated by using iodo- and bromosilanes and chlorofluorosilanes.
- Kunai, Atsutaka,Ohshita, Joji
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- Ring-opening iodo- and bromosilation of lactones for the formation of silyl haloalkanoates
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Ring-opening halosilation of lactones with two types of reagents, Et3SiH/MeI(PdCl2) (1a) and Et3SiH/AllylBr(PdCl2) (1b), was studied. Cyclic esters such as γ-butyrolactones, δ-valerolactone, and 6-hexanolide reacted with 1 equiv of 1a,b to give triethylsilyl ω-iodo- and ω-bromoalkanoates in good yields. Reaction of an acyclic ester, methyl benzoate, with 1a afforded triethylsilyl benzoate. O-Silyl-protected amino acids could be obtained by amination of the halosilation products, triethylsilyl ω-bromoalkanoates.
- Iwata, Arihiro,Ohshita, Joji,Tang, Heqing,Kunai, Atsutaka,Yamamoto, Yasushi,Matui, Chinami
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p. 3927 - 3929
(2007/10/03)
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- Triorganomonohalogenosilane
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A triorganomonohalogenosilane is prepared by reacting a triorganomonohydrosilane represented by the following general formula (I): with a halogenated allyl compound represented by the following general formula (II): STR1 in the presence of metal palladium, or a salt or complex of palladium to replace the hydrogen atom directly bonded to the silicon atom of the triorganomonohydrosilane with a halogen atom. In Formula ( I ), the substituents R1 's directly bonded to the silicon atom may be identical to or different from one another and each represents a monovalent organic group. In Formula (II), the substituents R2 's may likewise be identical to or different from one another and each represents a hydrogen atom or a monovalent alkyl group and X represents a chlorine atom, a bromine atom or an iodine atom.
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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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