scholarly journals Gold-Catalyzed Intramolecular Allylation of Silyl Alkynes Induced by Silane Alcoholysis

2006 ◽  
Vol 128 (33) ◽  
pp. 10664-10665 ◽  
Author(s):  
Sangho Park ◽  
Daesung Lee
Keyword(s):  

ChemInform ◽  
2003 ◽  
Vol 34 (25) ◽  
Author(s):  
Darby R. Schmidt ◽  
Steven J. O'Malley ◽  
James L. Leighton


2002 ◽  
Vol 124 (35) ◽  
pp. 10508-10518 ◽  
Author(s):  
Mee-Kyung Chung ◽  
Galina Orlova ◽  
John D. Goddard ◽  
Marcel Schlaf ◽  
Robert Harris ◽  
...  


ChemInform ◽  
2008 ◽  
Vol 39 (35) ◽  
Author(s):  
Patrizio Raffa ◽  
Claudio Evangelisti ◽  
Giovanni Vitulli ◽  
Piero Salvadori


Catalysts ◽  
2020 ◽  
Vol 10 (8) ◽  
pp. 908
Author(s):  
Katsuhiro Isozaki ◽  
Tomoya Taguchi ◽  
Kosuke Ishibashi ◽  
Takafumi Shimoaka ◽  
Wataru Kurashige ◽  
...  

The self-assembled monolayer (SAM)-modified metallic nanoparticles (MNPs) often exhibit improved chemoselectivity in various catalytic reactions by controlling the reactants’ orientations adsorbed in the SAM; however, there have been a few examples showing that the reaction rate, i.e., catalytic activity, is enhanced by the SAM-modification of MNP catalysts. The critical parameters that affect the catalytic activity, such as the supports, nanoparticle size, and molecular structures of the SAM components, remain uninvestigated in these sporadic literature precedents. Here, we report the mechanistic investigation on the effects of those parameters on the catalytic activity of alkanethiolate SAM-functionalized gold nanoparticles (AuNPs) toward silane alcoholysis reactions. The evaluation of the catalytic reaction over two-dimensionally arrayed dodecanethiolate SAM-functionalized AuNPs with different supports revealed the electronic interactions between AuNPs and the supports contributing to the rate enhancement. Additionally, an unprecedented size effect appeared—the AuNP with a 20 nm radius showed higher catalytic activity than those at 10 and 40 nm. Infrared reflection–absorption spectroscopy revealed that the conformational change of alkyl chains of the SAM affects the entrapment of reactants and products inside the SAM, and therefore brings about the acceleration effect. These findings provide a guideline for further applying the SAM-functionalization technique to stereoselective organic transformations with designer MNP catalysts.



2001 ◽  
Vol 79 (5-6) ◽  
pp. 949-957 ◽  
Author(s):  
Mee-Kyung Chung ◽  
George Ferguson ◽  
Valerie Robertson ◽  
Marcel Schlaf

The dimeric complex Ru2(µ-Cl)2Cl2(CO)4(PMe3)2 (1) forms an active silane alcoholysis complex in the polar solvent N,N-dimethylamino-acetamide (DMA). The dynamic behaviour of 1 in DMF-d7 solution has been investigated by variable temperature (VT) 1H NMR. The solid state structures of 1 and cis,cis,trans-RuCl2(CO)2(PMe3)2 (3) have been determined by single crystal X-ray diffractometry. Using ethylene glycol - triethylsilane as a model system, the catalytic activity of 1 in DMA is compared to that of a series of known silane alcoholysis catalysts, including RhCl(PPh3)3, PdX2 (X = Cl-, OAc-), and cis,cis,trans-[IrH2S2L2]SbF6 (L = PPh3, S = THF). Complex 3 is not an active silane alcoholysis catalyst in this solvent, but is active in nonpolar solvents. Its structure and spectroscopic signature is, however, different from that of a previously reported catalyst of the same composition.Key words: silane alcoholysis, polar solvent, ruthenium catalyst.



2000 ◽  
Vol 609 (1-2) ◽  
pp. 95-103 ◽  
Author(s):  
Xinggao Fang ◽  
Jean Huhmann-Vincent ◽  
Brian L. Scott ◽  
Gregory J. Kubas


2008 ◽  
Vol 49 (20) ◽  
pp. 3221-3224 ◽  
Author(s):  
Patrizio Raffa ◽  
Claudio Evangelisti ◽  
Giovanni Vitulli ◽  
Piero Salvadori


ChemInform ◽  
2008 ◽  
Vol 39 (15) ◽  
Author(s):  
Andrea Biffis ◽  
Marino Basato ◽  
Marianna Brichese ◽  
Luca Ronconi ◽  
Cristina Tubaro ◽  
...  
Keyword(s):  


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