- Gem-Heterosubstituted (stannyl)methylsilanes as synthetic equivalents of functionalized α-stannyl(methyl) anions
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α-Heterosubstituted silyl derivatives, such as phenylthio-, phenylseleno- and benzotriazolyl-stannyl silanes, react with aldehydes under tetra-n-butylammonium fluoride (TBAF) catalysis, leading to α-substituted-βhydroxy stannanes, able to behave as precursors of Z- and E-olefins, generated by deoxystannylation. This reactivity shows the capability of such heterosubstituted silanes to act as masked carbanions through a mild functionalization of the carbon-silicon bond.
- Tanini, Damiano,Nocentini, Tiziano,Capperucci, Antonella
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- Homologation of halostannanes with carbenoids: a convenient and straightforward one-step access to α-functionalized organotin reagents
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A direct, single synthetic homologative transformation of halostannanes into mono- or di-substituted methyl analogues is documented. Critical for the success of the operation is the excellent nucleophilicity of carbenoid-like methyllithium reagents (LiCHXY, X, Y = halogen, OR, and CN): by simply individuating the reagents' substitution pattern, the desired functionalized fragment is delivered to the electrophile. The wide scope of the protocol is evidenced also in the case of analogous halogermanium compounds. The tandem homologation-quenching with nucleophiles and the use of α-chloroallyllithium is also discussed.
- Touqeer, Saad,Castoldi, Laura,Langer, Thierry,Holzer, Wolfgang,Pace, Vittorio
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supporting information
p. 10112 - 10115
(2018/09/13)
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- Silyl-substituted dithioles as candidates for new electron donors
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Molecular orbital calculations revealed that the introduction of a silyl group onto the 2-position of 1,3-dithiole caused significant decrease of the ionization potential and that 2-silyl-1,3-dithioles served as a pseudo π-electron system. The silyl group could also be utilized as a bridge for linking π-electron systems to achieve artificial stacking. These concepts led us to the design and synthesis of silyl-substituted 1,3-benzodithioles as candidates for new electron donors. The oxidation potential of monosilyl-substituted 1,3-benzodithiole was found to be significantly less positive than that of the parent 1,3-benzodithiole. The introduction of the second silyl group caused further decrease of the oxidation potential. Compounds composed of two 1,3-benzodithiole units linked by a silyl group were also synthesized. These showed comparable oxidation potentials to those of the corresponding monomeric compounds. The effect of stannyl-substitution onto the 2-position of 1,3-dithiole was found to be larger than that of silyl-substitution. The effects of silyl-1 and stannyl-substitution for related systems such as thioanisole and 1,3-dithiane were also studied.
- Li,Nishiwaki,Itami,Yoshida
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p. 1717 - 1725
(2007/10/03)
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- Novel organotin herbicidal compounds
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Disclosed are novel organotin compounds and a process for preparing same. These organotin compounds correspond to the general formula: where R is alkyl of from 1 to 14 carbon atoms; aryl; or substituted aryl; and each R' is alkyl of 1 to 14 carbon atoms.
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