Synthetic Applications of Substitution and Addition Reactions Promoted by Cerium(IV) Ammonium Nitrate

  • Enrico Baciocchi
  • Renzo Ruzziconi
Part of the NATO ASI Series book series (ASIC, volume 260)

Abstract

Cerium(IV) salts, and expecially cerium(IV) ammonium nitrate, (CAN), are very efficient in promoting a highly selective side-chain functionalization of methylbenzenes. With CAN the process leads to aromatic aldehydes and benzyl derivatives, depending on the reaction conditions. In di- and polymethylbenzenes selective functionalization of the methyl group with electron donating substituents at the ortho and (or) para position is possible.

Reactivity can significantly be increased by adding Br-, at the expense, however, of selectivity, which is significantly reduced since the attacking species is now Br*. Both selectivity and reactivity are instead very high in the photochemical reaction of CAN with methylbenzenes in MeCN leading to benzyl nitrates; the reacting species is NO3•, formed by photolysis of CAN. The reaction can be extended to cycloalkanes and moreover, if carried out in the presence of dioxygen, made catalytic in CAN.

CAN in AcOH is also a very useful reactant for ring functionalization (formation of phenyl acetates or quinones) of aromatic compounds. In methylaromatics nuclear attack can be the favored process in the presence of electron donating substituents meta to the methyl group. With alkenylaromatic compounds CAN leads to 1,2-dinitrate adducts in good yield. Under irradiation the reaction becomes much faster and can also be extended to unactivated alkenes.

Reaction of CAN with carbonyl compounds forms electrophilic α-keto carbon radicals which can promote homolytic aromatic substitutions or add to alkenes to give addition products where the formation of a new carbon carbon bond is accompanied by the introduction of the nitrate group, which can undergo further functionalization. Among the homolytic aromatic substitutions, malonylation is very useful expecially with heteroaromatic compounds. The addition reactions to alkenes (particularly, conjugated dienes, styrenes, vinyl acetates) allow the synthesis of a variety of compounds (vinylcyclopropanes, 1,4-disubstituted trans-2-butenes, 1,4-dicarbonyl compounds, diydrofurans and furans) to be carried out.

Keywords

Radical Cation Carbonyl Compound Vinyl Acetate Nitrate Group Substrate Molar Ratio 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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Copyright information

© Kluwer Academic Publishers 1989

Authors and Affiliations

  • Enrico Baciocchi
    • 1
    • 2
  • Renzo Ruzziconi
    • 1
    • 2
  1. 1.Department of ChemistryUniversity of Rome “La Sapienza”RomaItaly
  2. 2.Department of ChemistryUniversity of PerugiaPerugiaItaly

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