Rhodium-Catalyzed Silylcarbocyclization (SiCaC) and Carbonylative Silylcarbocyclization (CO-SiCaC) Reactions of Enynes was written by Ojima, Iwao;Vu, An T.;Lee, Seung-Yub;McCullagh, James V.;Moralee, Andrew C.;Fujiwara, Masaki;Hoang, Tram H.. And the article was included in Journal of the American Chemical Society in 2002.Application In Synthesis of Diethyl 2-(prop-2-yn-1-yl)malonate This article mentions the following:
The reaction of a 1,6-enyne with a hydrosilane catalyzed by Rh(acac)(CO)2, Rh4(CO)12, or Rh2Co2(CO)12 under ambient CO atm. or N2 gives 2-methyl-1-silylmethylidene-2-cyclopentane or its heteroatom congener in excellent yield through Silylcarbocyclization (SiCaC) process. The same reaction, but in the presence of a phosphite such as P(OEt)3 and P(OPh)3 under 20 atm of CO, affords the corresponding 2-formylmethyl-1-silylmethylidene-2-cyclopentane or its heteroatom congener with excellent selectivity through carbonylative silylcarbocyclization (CO-SiCaC) process. The SiCaC reaction also was applied to a 1,6-enyne bearing a cyclohexenyl group as the alkene moiety and a 1,7-enyne system. The functionalized five- and six-membered ring systems obtained by these novel cyclization reactions serve as useful and versatile intermediates for the syntheses of natural and unnatural heterocyclic and carbocyclic compounds Possible mechanisms for the SiCaC and CO-SiCaC reactions as well as unique features of these processes are discussed. In the experiment, the researchers used many compounds, for example, Diethyl 2-(prop-2-yn-1-yl)malonate (cas: 17920-23-9Application In Synthesis of Diethyl 2-(prop-2-yn-1-yl)malonate).
Diethyl 2-(prop-2-yn-1-yl)malonate (cas: 17920-23-9) belongs to esters. Esters are widespread in nature and are widely used in industry. In nature, fats are in general triesters derived from glycerol and fatty acids. Esters are responsible for the aroma of many fruits. Esters contain a carbonyl center, which gives rise to 120° C–C–O and O–C–O angles. Unlike amides, esters are structurally flexible functional groups because rotation about the C–O–C bonds has a low barrier. Their flexibility and low polarity is manifested in their physical properties; they tend to be less rigid (lower melting point) and more volatile (lower boiling point) than the corresponding amides. Application In Synthesis of Diethyl 2-(prop-2-yn-1-yl)malonate
Referemce:
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics