292081-07-3Relevant academic research and scientific papers
Synthesis of 2-substituted benzofurans and indoles using functionalized titanium benzylidene reagents on solid phase
Macleod, Calum,McKiernan, Gordon J.,Guthrie, Emma J.,Farrugia, Louis J.,Hamprecht, Dieter W.,Macritchie, Jackie,Hartley, Richard C.
, p. 387 - 401 (2007/10/03)
Titanium(IV) benzylidenes bearing a masked oxygen or nitrogen nucleophile in the ortho position were generated from thioacetals, using low-valent titanocene complex, Cp2Ti[P(OEt)3]2. Methylene acetal, alkyl ether, silyl ether, fluoro, tertiary amino, and N-alkyl, N-benzyl, N-prenyl, and N-silyl tert-butyl carbamate groups were tolerated in the titanium alkylidene reagents (Schrock carbenes). Aryl-chlorine bonds were stable to the titanium benzylidene functionality, but there was poor chemoselectivity for the reduction of the thioacetal in the presence of an aryl chloride. The titanium benzylidenes converted Merrifield and Wang resin-bound esters into enol ethers. The oxygen nucleophile was masked as a TMS ether, and when the resin-bound enol ethers bearing this ortho substituent were treated with 1% TFA in dichloromethane, benzofurans were released from resin in high yields. The chameleon catch strategy ensured excellent purity. In a similar way, N-alkylated and N-silylated tert-butyl carbamates were used for the synthesis of N-alkyl and N-Boc indoles, respectively. These traceless solid-phase syntheses of heterocycles are believed to involve post-cleavage modification rather than cyclative termination.
Alkylidenation of esters on solid support and traceless synthesis of 2- substituted benzofurans
Guthrie, Emma J.,MacRitchie, Jackie,Hartley, Richard C.
, p. 4987 - 4990 (2007/10/03)
Polymer-supported esters are smoothly converted into enol ethers using a titanocene alkylidene prepared by treatment of 2-tert- butyldimethylsilyloxybenzaldehyde diphenyldithioacetal with the low valent titanium species Cp2Ti[P(OEt)3]2. Treatment of the enol ethers with acid leads to the release of ketones from the Wang resin in high yield. Traceless solid-phase synthesis of 2-substituted benzofurans is achieved in a three- step termination procedure. (C) 2000 Published by Elsevier Science Ltd.
