1781-83-5Relevant articles and documents
Sands,Botteron
, p. 2690 (1963)
Palladium catalyzed synthesis of some novel (Spirocycloalkenyl) trimethylsilylacetylenes
Venkatesha, Manjunatha Achanna,Suresh, HariPrasad
, p. 457 - 461 (2013/08/23)
The synthesis of some novel (spirocycloalkenyl)trimethylsilylacetylenes employing the Sonogashira coupling reaction of the corresponding novel spirocycloalkenyliodides with trimethylsilylacetylene and Pd(PPh3)2Cl2/CuI catalyst in yields ranging 79-84% is reported. The compounds would serve as novel (spirocycloalkenyl)acetylenic anionic synthons.
Zirconium complexes bearing η5-5′,6′,7′- trihydrospiro[cycloalkane-1,4′-indenyl] ligands
Asachenko, Andrey F.,Kononovich, Dmitry S.,Zharov, Andrey N.,Razavi, Abbas,Voskoboynikov, Alexander Z.
experimental part, p. 1940 - 1948 (2010/09/16)
Tetrahydroindenes including spiro-cyclopentyl and -cyclohexyl fragments were successfully synthesized either via base-catalyzed cyclization of the respective γ-diketone or via acid-catalyzed Nazarov cyclization of the corresponding divinylketones. These substituted cyclopentadienes were metallated with nBuLi. The following reaction of the lithium salts with Cp (*)ZrCl3 gave three novel zirconocenes bearing spiro-cycloalkane fragments. One of these complexes, (η5- 5′,6′,7′-trihydrospiro[cyclohexane-1,4′-(2- methylindenyl)])(η5-pentamethyl-cyclopentadienyl)zirconium dichloride, has been characterized by X-ray crystal structure analysis. Tetrahydroindenes including spiro-cyclopentyl and -cyclohehyl fragments were successfully synthesized either via base-catalyzed cyclization of the respective γ-diketone or via acid-catalyzed Nazarov cyclization of the corresponding divinylketones. These substituted cyclopentadienes were metallated with nBuLi. The following reaction of the lithium salts with Cp (*)ZrCl3 gave three novel zirconocenes bearing spiro-cycloalkane fragments.
Palladium-catalyzed intramolecular hydroalkylation of alkenyl- β-keto esters, α-aryl ketones, and alkyl ketones in the presence of Me 3SiCl or HCI
Han, Xiaoqing,Wang, Xiang,Pei, Tao,Widenhoefer, Ross A.
, p. 6333 - 6342 (2007/10/03)
Reaction of 3-butenyl β-keto esters or 3-butenyl α-aryl ketones with a catalytic amount of [PdCl2(CH3CN)2] (2) and a stoichiometric amount of Me3SiCl or Me3SiCl/ CuCl2 in dioxane at 25-70°C formed 2-substituted cyclohexanones in good yield with high regioselectivity. This protocol tolerated a number of ester and aryl groups and tolerated substitution at the allylic, enolic, and cis and trans terminal olefinic positions. In situ NMR experiments indicated that the chlorosilane was not directly involved in palladium-catalyzed hydroalkylation, but rather served as a source of HCl, which presumably catalyzes enolization of the ketone. Identification of HCl as the active promoter of palladium-catalyzed hydroalkylation led to the development of an effective protocol for the hydroalkylation of alkyl 3-butenyl ketones that employed sub-stoichiometric amounts of 2, HCl, and CuCl2 in a sealed tube at 70°C.
