Normal-iso rearrangement in cyanotrialkylsilanes

Seckar, Joel A.; Thayer, John S.

doi:10.1021/ic50157a001

Cited by 62 publications

(33 citation statements)

References 3 publications

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“…We investigated the adsorption of TMSCN onto gold thin films by using IR spectroscopy (Figure 3). For free TMSCN molecules, the CN stretching was observed at 2191 cm −1 , which was consistent with the reported value 25. When a gold thin film immersed in the TMSCN solution (CDCl 3 phase) was taken out, rinsed with chloroform, and analyzed by IR spectroscopy, the peak of the CN stretching appeared at 2156 cm −1 .…”

Section: Resultssupporting

confidence: 90%

Gold‐Catalyzed Cyanosilylation Reaction: Homogeneous and Heterogeneous Pathways

Cho

Lee

Kang

et al. 2007

Chemistry A European J

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Gold had been considered to be an extremely inert metal, but recently it was found that nanometer-sized gold particles on metal-oxide supports acted as catalysts for simple organic reactions, such as oxidation and hydrogenation, even at or below room temperature. Herein, we report that gold nanoparticles (AuNPs) of zero oxidation state (Au0) are catalytically active for a C--C bond-forming reaction, the cyanosilylation of aldehydes. The AuNP-catalyzed cyanosilylation proceeded smoothly at room temperature with 0.2 wt % loading of AuNPs. The reactions of aromatic aldehydes were almost quantitative, except for benzaldehyde derivatives containing the electron-withdrawing NO2 group, and alpha,beta-unsaturated aromatic aldehydes were the most reactive substrates. The reactions also went smoothly for aliphatic aldehydes. Mechanistic studies indicated that the reactions proceeded both homogeneously and heterogeneously: homogeneous catalysis by leached gold species and heterogeneous catalysis by the adsorption of the reactants (aldehydes and trimethylsilyl cyanide) onto AuNPs. The ratio of homogeneous and heterogeneous catalysis was estimated to be approximately 4:1.

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Section: Resultssupporting

confidence: 90%

Gold‐Catalyzed Cyanosilylation Reaction: Homogeneous and Heterogeneous Pathways

Cho

Lee

Kang

et al. 2007

Chemistry A European J

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“…Theoretical calculation suggests that the cyanide is more stable than the isocyanide. This is in accord with the experimental fact that trimethylsilyl cyanide is thermodynamically more favorable [26].…”

Section: Theoretical Approachsupporting

confidence: 88%

Strong bond cleavage promoted by silyl group migration in a coordination sphere

Nakazawa

2011

WIT Transactions on Ecology and the Environment

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C-CN bond cleavage in organonitriles was attained in the photoreaction with HSiEt 3 in the presence of a catalytic amount of ( 5 -C 5 H 5 )Fe(CO) 2 Me. The reaction sequence was proposed, where silyl migration from Fe to N in the coordinating nitrile is a key step. DFT calculations proposed a silyl migration with small activation energy of 4.0 kcal/mol and subsequent C-CN bond cleavage on the Fe coordination sphere. N-CN bond cleavage in cyanamide (R 2 NCN) was also attained by a transition metal catalyst. A catalytic cycle was proposed where a silyl migration from a transition metal to the nitrile nitrogen is involved. An N-silylated  2 -amidino complex was isolated, which was shown to be an intermediate in the catalytic pathway.

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“…[11] However, the formation of Me 3 SiNC is rather slow in solution (albeit in 1-chloronaphthalene rather than MeCN), thus taking approximately 10 minutes at 225 8C to reach an approximate concentration of 0.15 % relative to that of the cyano isomer. [12] It is therefore reasonable to conclude that this equilibrium would be reached even more slowly at room temperature, thus suggesting that the provenance of the isocyano isomers 1 e and 1 f and, through their isomerization, the cyano isomers 1 g and 1 h, respectively, is Me 3 SiCN and not Me 3 SiNC because of the almost instantaneous formation of 1 e and 1 f at room temperature.…”

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confidence: 99%