1598424-36-2Relevant academic research and scientific papers
PROCESS FOR THE RUTHENIUM CATALYZED TRANS-SELECTIVE HYDROSTANNATION OF ALKYNES
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Page/Page column 23; 24; 30; 32, (2015/05/06)
The present invention refers to a process for the ruthenium-catalyzed trans-selective hydrostannation of alkynes and the so-obtained products. The inventive process makes use of a tin hydride which is reacted with an alkyne in the presence of a cyclopentadienyl-coordinated ruthenium catalyst.
Interligand interactions dictate the regioselectivity of trans-hydrometalations and related reactions catalyzed by [Cp?RuCl]. Hydrogen bonding to a chloride ligand as a steering principle in catalysis
Rummelt, Stephan M.,Radkowski, Karin,Ro?ca, Drago?-Adrian,Fürstner, Alois
supporting information, p. 5506 - 5519 (2015/05/13)
Reactions of internal alkynes with R3M-H (M = Si, Ge, Sn) follow an unconventional trans-addition mode in the presence of [Cp?Ru(MeCN)3]PF6 (1) as the catalyst; however, the regioselectivity is often poor with unsymmetrica
Ruthenium-catalyzed trans-selective hydrostannation of alkynes
Rummelt, Stephan M.,Fuerstner, Alois
supporting information, p. 3626 - 3630 (2014/04/17)
In contrast to all other transition-metal-catalyzed hydrostannation reactions documented in the literature, the addition of Bu3SnH across various types of alkynes proceeds with excellent trans selectivity, provided the reaction is catalyzed by [CpRu]-based complexes. This method is distinguished by a broad substrate scope and a remarkable compatibility with functional groups, including various substituents that would neither survive under the conditions of established Lewis acid mediated trans hydrostannations nor withstand free-radical reactions. In case of unsymmetrical alkynes, a cooperative effect between the proper catalyst and protic functionality in the substrate allows outstanding levels of regioselectivity to be secured as well. Unorthodox: Ruthenium catalysts allow stannanes to be added in a trans fashion across the triple bonds of terminal, internal, silylated, and chlorinated alkynes. This pattern violates the basic mechanism of transition-metal catalysis which otherwise secures high cis selectivity in hydrometalations. Cooperative effects between the ruthenium species and protic functionality render reactions of unsymmetrical substrates regioselective. Cp=η5-C 5Me5.
