- Tandem Insertion/[3,3]-Sigmatropic Rearrangement Involving the Formation of Silyl Ketene Acetals by Insertion of Rhodium Carbenes into S-Si Bonds
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Allyl 2-diazo-2-phenylacetates are shown to react with trimethylsilyl thioethers in the presence of rhodium(II) catalysts to generate α-allyl-α-thio silyl esters. The transformation involves a tandem process involving formal rhodium-catalyzed insertion of the carbene group into the S-Si bond to generate a silyl ketene acetal, followed by a spontaneous Ireland-Claisen rearrangement. The silyl ester products were isolated as the corresponding carboxylic acids after aqueous workup. Intramolecular cyclopropanation of the allyl fragment generally competes with addition of the heteroatom to the carbene center. The reaction occurs under mild conditions and in high yield, allowing for rapid entry into rearrangement tetrasubstituted products. Propargyl esters were shown to generate the corresponding α-allenyl products.
- Combs, Jason R.,Lai, Yin-Chu,Van Vranken, David L.
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supporting information
p. 2841 - 2845
(2021/05/05)
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- Copper-Catalyzed Three-Component Coupling Reaction of Aryl Iodides, a Disilathiane, and Alkyl Benzoates Leading to a One-Pot Synthesis of Alkyl Aryl Sulfides
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A copper-catalyzed three-component coupling reaction of aryl iodides, hexamethyldisilathiane and alkyl benzoates leading to alkyl aryl sulfides has been demonstrated. A disilathiane acted as both a sulfur source and a promoter of the sulfidation, and the alkyl moiety of the alkyl benzoate was effectively introduced on one side of the sulfide. Moreover, we found that the protocol can be expanded to the preparation of ethyl phenyl selenide with diphenyl diselenide.
- Sakai, Norio,Maeda, Hiromu,Ogiwara, Yohei
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p. 2323 - 2330
(2019/05/24)
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- Synthesis of a wide range of thioethers by indium triiodide catalyzed direct coupling between alkyl acetates and thiosilanes
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An indium triiodide-catalyzed substitution of the acetoxy group in alkyl acetates with thiosilanes provides access to a variety of thioethers. The method is efficient for a wide scope of acetates such as primary alkyl, secondary alkyl, tertiary alkyl, allylic, benzylic, and propargylic acetates.
- Nishimoto, Yoshihiro,Okita, Aya,Yasuda, Makoto,Baba, Akio
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supporting information; experimental part
p. 1846 - 1849
(2012/06/18)
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- Thioether complexes of tungsten hexacarbonyl
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The preparation of a series of organic and organometallic thioethers R3MSR' (M = C,Si,Ge, or Sn) is reported.From these, several new compounds of type 1 are synthesized, some of which contain para-substituted aryl functions for R and R'.In hexane solution in the carbonyl streching region of the ir the uv there is evidence for a degree of multiple bonding, at least in the M - S - WW - CO portion of these molecules.Multiple bonding extending into aromatic R or R'is small or non-existent and cannot be assessed precisely because of spontaneous decomposition of the complexes.All the complexes undergo a thermally initiated decomposition, the case of which depends on the nature of R, R', and M.The unusual W(I) thiolate cis-2 is the termal decomposition product.
- Lucas, C. Robert
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p. 1758 - 1763
(2007/10/02)
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- Synthesis, Structure, and Catalytic Activity of μ-Alkylthio- and μ-Arylthio-μ-chloro-dicarbonylbis(tri-tert-butylphosphane)dirhodium Complexes
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Tetracarbonyldi-μ-chloro-dirhodium (1) reacts with tri-tert-butylphosphane and alkyl or aryl trimethylsilyl sulfides 4 to give complexes tBu3)2Cl(SR)> (5a-i).The complexes 5h,i with the surface active trialkoxysilyl groups are fixed onto a fused silica support.The X-ray structural analyses of tBu3)2Cl(StBu)> (5c) and tBu3)2Cl(SC6H4Cl)> (5g) indicate a cis-configuration of the tri-tert-butylphosphane ligands.The new complexes catalyze the isomerization of 1-octen-3-ol (10) into 3-octanone (11), of 4-allylanisole (12) into cis- and trans-4-(1-propenyl)anisole (13), of trans-stilbene oxide (14) into desoxybenzoin (15), the transfer hydrogenation of α,β-unsaturated ketones by formic acid (16 -> 17), and the transfer hydrogenolysis of trihalomethyl compounds (18, 20) by halogen free alcohols.
- Schumann, Herbert,Cielusek, Guy,Jurgis, Stanislaw,Hahn, Ekkehardt,Pickardt, Joachim,et al.
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p. 2825 - 2838
(2007/10/02)
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