190852-46-1Relevant academic research and scientific papers
Geometric E→Z Isomerisation of Alkenyl Silanes by Selective Energy Transfer Catalysis: Stereodivergent Synthesis of Triarylethylenes via a Formal anti-Metallometallation
Fa?bender, Svenja I.,Molloy, John J.,Mück-Lichtenfeld, Christian,Gilmour, Ryan
, p. 18619 - 18626 (2019/11/16)
An efficient geometrical E→Z isomerisation of alkenyl silanes is disclosed via selective energy transfer using an inexpensive organic sensitiser. Characterised by operational simplicity, short reaction times (2 h), and broad substrate tolerance, the reaction displays high selectivity for trisubstituted systems (Z/E up to 95:5). In contrast to thermal activation, directionality results from deconjugation of the π-system in the Z-isomer due to A1,3-strain thereby inhibiting re-activation. The structural importance of the β-substituent logically prompted an investigation of mixed bis-nucleophiles (Si, Sn, B). These versatile linchpins also undergo facile isomerisation, thereby enabling a formal anti-metallometallation. Mechanistic interrogation, supported by a theoretical investigation, is disclosed together with application of the products to the stereospecific synthesis of biologically relevant target structures.
Rhodium complexes of PCNHCP: Oxidative addition of dichloromethane and catalytic hydrosilylation of alkynes affording (E)-alkenylsilanes
Zeng, Jing Yao,Hsieh, Meng-Hua,Lee, Hon Man
, p. 5662 - 5671 (2007/10/03)
New rhodium complexes of PCNHCP have been synthesized by using the silver transfer reagent, [Ag3(PCNHCP) 2Cl]Cl2 (2). In the reaction between 2 and [Rh(COD)Cl]2 in dichloromethane, the pres
Dehydrogenative silylation of terminal alkynes by iridium catalyst
Shimizu, Rie,Fuchikami, Takamasa
, p. 907 - 910 (2007/10/03)
Dehydrogenative silylation of terminal alkynes with hydrosilanes proceeds in the presence of iridium catalyst to afford the corresponding silylacetylenes. When phenylacetylene and triethylsilane were heated in dry DME in the presence of Ir4(CO)12-PPh3, (2-phenylethynyl)triethylsilane was obtained in 96% yield with little of hydrosilylated products. The present method is applicable for a variety of terminal alkynes and hydrosilanes to give the corresponding silylacetylenes in good yields with high selectivities. (C) 2000 Elsevier Science Ltd.
