Multicomponent Reactions Among Alkyl Isocyanides, sp reactants, and sp2 Carbon Cages

We explored the reactivity and substrate scope of the reactions among an alkyl isocyanide, an sp-hybridized reactant (i.e. alkyne or allene), and a carbon cage, as a new approach to functionalize fullerenes and metallofullerenes. This account summarizes the key findings in our recent published work, and some original data for the reaction involving an isocyanide, allenes, and metallofullerene Lu3N@C80.

One-pot synthesis of Acanthus ilicifolius Linn alkaloid 2-benzoxazolinone derivatives via a tandem Ugi 4-component coupling/haloform cyclization

A one-pot, base-mediated approach to Acanthus ilicifolius Linn alkaloid 2-benzoxazolinone derivatives is developed. Starting from trichloroacetic acid, o-aminophenol, substituted benzaldehydes and alkyl isocyanides, the desired 2-benzoxazolinone derivatives are obtained in good yields via a tandem Ugi condensation and intramolecular haloform cyclization at room temperature in the presence of Et3N.

Systematic reductive oligomerization of isocyanides with a vanadium(ii) complex

The vanadium(ii) complex is shown to mediate reductive oligomerization of aryl isocaynides, leading to formation of a dimer, trimers, and tetramers. The analogous reaction with alkyl isocyanides results in C–NC bond cleavage.

A New Method for the Preparation of Bis(alkylamino)maleonitriles from Aliphatic Isocyanides with TMSCN and Bi(OTf)3

Bis(alkylamino)maleonitriles are starting materials for the synthesis of a number of important intermediates, including porphyrazines that serve as dyes, pigments, and models of biologically active substances; hence, the development of improved methods for their preparation is important. Herein, we report a facile new method for the preparation of bis(alkylamino)maleonitriles from isocyanides. Treatment of tert-alkyl isocyanides with trimethylsilyl cyanide (TMSCN) and trimethylsilyl triflate (TMSOTf) in the presence of bismuth(III) triflate [Bi(OTf)3] afforded the corresponding bis(alkylamino)maleonitriles in moderate yields. tert-Alkyl isocyanides bearing a variety of functional groups, including halide, ether, ester, imide, amide, and carbamate, are tolerated under the developed reaction conditions. To the best of our knowledge, this is the first report of a synthetic method for the preparation of bis(alkylamino)maleonitriles in a single step from tertiary alkyl isocyanides.

Reaction Between 7-Hydroxy Coumarin, Alkyl Isocyanides and Dialkyl Acetylenedicarboxylate: Synthesis of 4H-Chromenes and 1-Azabuta-1,3-dienes

The reactive intermediate generated by the addition of <em>tert</em>-butyl and 1,1,3,3-tetramethyl butyl isocyanide to dialkyl acetylenedicarboxylate was trapped by 7-hydroxycoumarin to produce highly functionalized 4<em>H</em>-chromenes in fairly good yields. When the reaction is performed with cyclohexyl isocyanide, 1-azabuta-1,3-dienes were obtained.

Alkyl Isocyanides Promoted Synthesis of Functionalized Azadienes from Dialkyl Acetylene Dicarboxylates and N-Hydroxysuccinimide

The reaction between N-Hydroxy succinimide with dialkyl acetylene dicarboxylates in the presence of isocyanides, leads to functionalized azadienes in good yields. The product were analized and the structures of reaction compounds were deduced from their IR, 1HNMR and 13CNMR spectra.