- Synthesis of Benzosiloles by Intramolecular anti-Hydroarylation via ortho-C-H Activation of Aryloxyethynyl Silanes
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Straightforward synthesis of benzosiloles was achieved by the invention of Pd/acid-catalyzed intramolecular anti-hydroarylation of aryloxyethynyl(aryl)silanes via ortho-C-H bond activation. The aryloxy group bound to the ethynyl carbon is the key factor for this transformation.
- Minami, Yasunori,Noguchi, Yuta,Hiyama, Tamejiro
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supporting information
p. 14013 - 14016
(2017/10/17)
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- Mechanistic study on the base-promoted reaction of allylphenylsilanes to alkenylsilanols
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On treatment of allylphenylsilanes with t-BuOK and 18-crown-6 in DMSO, isomerization of the olefinic double bond and subsequent substitution of the phenyl group with a hydroxy group took place smoothly to afford alkenylsilanol derivatives in good yields. The reaction mechanism was investigated using 18O-labeled sulfoxide. We found that a (methylsulfinyl)methyl anion generated from DMSO participated in this reaction.
- Imazeki, Shigeaki,Sugawara, Hiroo,Sano, Atsunori,Akiyama, Takahiko
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experimental part
p. 623 - 629
(2009/04/11)
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- Modular approach to silicon-bridged biaryls: Palladium-catalyzed intramolecular coupling of 2-(arylsilyl)aryl triflates
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(Chemical Equation Presented) Bridge of Si: Intramolecular direct arylation of 2-(arylsilyl)aryl triflates is catalyzed smoothly by Pd(OAc) 2/PCy3 in the presence of Et2NH in dimethylacetamide (DMA), giving rise to the corresponding silicon-bridged biaryls in good to excellent yields. The new approach has led to the synthesis of a silicon-bridged 2-phenylindole (see scheme) that exhibits blue photoluminescence in the solid state with extremely high quantum yields.
- Shimizu, Masaki,Mochida, Kenji,Hiyama, Tamejiro
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supporting information; body text
p. 9760 - 9764
(2009/05/30)
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- Intramolecular [3+2]-hetero-annulation of allylsilanes with 1,3-cyclohexanediones and its application in the synthesis of hexacyclic hopane triterpenes
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In this letter we describe the intramolecular [3+2]-hetero-annulation of allylsilanes with 1,3-cyclohexanediones followed by sila-Wagner-Meerwein shift. The new synthesis of the cyclization precursors offers the advantage to vary the silyl terminator at t
- Schinzer,Muller,Fischer,Priess
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p. 1265 - 1268
(2007/10/03)
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- Preparation of 2,5-anhydrohexitols (part I). Silicon-directed stereocontrolled cyclization
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Stereoselective chain-extension of carbohydrate aldehydes with the hydroxymethylating reagent (dimethylphenylsilyl)methylmagnesium chloride (1) followed by acid-mediated cyclization gives access to 2,5-anhydro-hexitols. The stereoselectivity of the ring closure depends on the nature of the acid, i.e., treatment with excess BF3·Et2O or catalytic H2SO4 leads to tetrahydrofurans with 2,3-cis or 2,3-trans configuration, respectively. Concomitant elimination is effectively suppressed in case of cyclisation of the more sterically hindered isopropyl substituted silanes.
- Van Delft, Floris L.,Valentijn, A. Rob P.M.,Van Der Marel, Gijs A.,Van Boom, Jacques H.
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p. 165 - 190
(2007/10/03)
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- Tandem [4 + 2]/[3 + 2] cycloadditions of nitroalkenes. 13. The synthesis of (-)-detoxinine
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(-)-Detoxinine, an unusual, highly-functionalized amino acid, is the core residue of many components that comprise the detoxin complex. The synthesis of (-)-detoxinine was accomplished in 10 steps and 13.4% overall yield from commercially available dichlorodiisopropylsilane. The key step is an asymmetric tandem inter [4 + 2]/intra [3 + 2] cycloaddition between silyoxynitroalkene 17 and chiral vinyl ether (-)-24, illustrating the application of a temporary silicon tether in the tandem nitroalkene cycloaddition process.
- Denmark, Scott E.,Hurd, Alexander R.,Sacha, Hubert J.
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p. 1668 - 1674
(2007/10/03)
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- AN ALTERNATIVE ROUTE TO PERALKYLCYCLOPOLYSILANES: THE REACTION OF 1,2-DICHLOROTETRAALKYLDISILANES WITH LITHIUM
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The reaction of 1,2-dichlorotetraalkyldisilanes, Cl(R1R2Si)2Cl (R1=R2=iPr; R1, R2=iPr, Me; R1, R2=Me3SiCH2, Me; R1, R2=tBuCH2, Me; R1, R2=tBu, Me), with an excess amount of lithium in tetrahydrofuran gave the corresponding peralkylcyclopolysilanes, n (n=4-5), under mild conditions.
- Watanabe, Hamao,Inose, Jun,Fukushima, Koji,Kougo, Yuichi,Nagai, Yoichiro
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p. 1711 - 1714
(2007/10/02)
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