1833-31-4Relevant articles and documents
Synthesis of C14-Desmethylene Corialactone D and Discovery of Inhibitors of Nerve Growth Factor Mediated Neurite Outgrowth
Leon, Robert M.,Ravi, Divya,An, Jennifer S.,Del Genio, Carmen L.,Rheingold, Arnold L.,Gaur, Arti B.,Micalizio, Glenn C.
, p. 3193 - 3197 (2019)
An asymmetric synthesis of C14-desmethylene corialactone D is described on the basis of strategic application of a metallacycle-mediated annulative cross-coupling reaction, a Still [2,3]-Wittig rearrangement, and Morken's hydroxyl-directed diboration reac
Synthesis of Cyclic Alkenyl Dimethylsiloxanes from Alkynyl Benzyldimethylsilanes and Application in Polyene Synthesis
Gudmundsson, Haraldur G.,Kuper, Christian J.,Cornut, Damien,Urbitsch, Felix,Elbert, Bryony L.,Anderson, Edward A.
, (2019/11/14)
Cyclic dimethylalkenylsiloxanes, useful motifs for (Z)-selective Hiyama cross-coupling, are accessed from alkynyl benzyldimethylsilanes featuring adjacent allylic or homoallylic oxygen substituents by semihydrogenation/debenzylation/cyclization. While formation of 5- and 6-membered rings can be achieved from the free alcohols using fluoride or silanolate, allylic acetate precursors to 5-membered rings display distinct modes of activation. The utility of these compounds is demonstrated through the preparation of a variety of (Z)-alkene-containing polyenes and application to a concise total synthesis of leukotriene B3.
Effect of the substituents at the silicon of (ω-chloroalkyl)silanes on the alkylation to benzene
Yoo, Bok Ryul,Hyun Kim, Jeong,Lee, Ho-Jin,Lee, Kang-Bong,Nam Jung, Il
, p. 239 - 245 (2007/10/03)
(ω-Chloroalkyl)silanes [Cl3-mMemSi(CH2)n-Cl: m=0-3, n=1-3] underwent Friedel-Crafts alkylation with benzene in the presence of aluminum chloride to give alkylated products. Such alkylation reactions took place at temperatures ranging from room temperature (m=0-1, n=2, 3; m=3, n=1) to 80 (m=1, 2; n=1) and 200°C (m=0; n=1), depending on the substituent(s) of the silicon and the alkylene-chain spacer between the silicon and C-Cl bond of (ω-chloroalkyl)silanes. In the alkylation to benzene, the reactivities of (ω-chloroalkyl)silanes increase as the number (m) of methyl-group(s) at the silicon and the alkylene length between the silicon and C-Cl bond increases. While decomposition of alkylation products was observed at two more methyl groups substituted at silicon in the cases of (chloromethyl)silanes such as (chloromethyl)dimethylchlorosilane and (chloromethyl)trimethylsilane. The reaction with (chloromethyl)trimethylsilane occurred at room temperature to give trimethylchlorosilane, toluene and xylene via a decomposition reaction of the products. No (trimethylsilylmethyl)benzene was formed. In the alkylation to benzene, the reactivity of (ω-chloroalkyl)silanes decreases in the following order: m=3>2>1>0; n=3>2?1. The results are consistent with the stability of the carbocation generated by the complexation of (ω-chloroalkyl)silanes with aluminum chloride.