Brønsted Acid Catalyzed Formal Insertion of Isocyanides into a C−O Bond of Acetals

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Abstract

The Brønsted acid catalyzed formal insertion of an isocyanide into a C−O bond of an acetal is described. A diverse array of acyclic and cyclic acetals can be applied to the catalytic insertion to form α-alkoxy imidates. Functional groups, such as nitro, cyano, halogen, ester, and alkoxy groups, are tolerant to the reaction conditions employed. The course of the reaction is highly dependent on the structure of the isocyanide. The use of an electron-deficient aryl isocyanide, such as 2c and 2d, is required to selectively obtain the monoinsertion product. When aryl isocyanides containing alkyl substituents, such as 2a and 2b, are employed, two molecules of the isocyanide are incorporated, and the double-insertion product is obtained. The reaction of tert-octyl isocyanide also induces a double incorporation, but the subsequent acid-mediated fragmentation leads to the 2-alkoxy imidoyl cyanide. The monoinsertion products, α-alkoxy imidates, can readily be hydrolyzed to α-alkoxy esters, realizing the formal carbonylation of an acetal.

Citing Articles

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This article has been cited by 8 ACS Journal articles (5 most recent appear below).

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  Switch in Stereoselectivity Caused by the Isocyanide Structure in the Rhodium-Catalyzed Silylimination of Alkynes

  Yoshiya Fukumoto , Motoyuki Hagihara , Fuyuko Kinashi , and Naoto Chatani
  Journal of the American Chemical Society 0 (ja),

  • Switch in Stereoselectivity Caused by the Isocyanide Structure in the Rhodium-Catalyzed Silylimination of Alkynes

    Yoshiya Fukumoto , Motoyuki Hagihara , Fuyuko Kinashi , and Naoto Chatani
    Journal of the American Chemical Society 0 (ja),

    The reaction of terminal alkynes with hydrosilanes and tert-alkyl isocyanides in the presence of Rh4(CO)12 gives Z-β-silyl-α,β-unsaturated imines in good yields. On the other hand, the use of aryl isocyanides in place of tert-alkyl isocyanides leads to ...

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• 

  Supported p-Toluenesulfonic Acid as a Highly Robust and Eco-Friendly Isocyanide Scavenger

  Jhonny Azuaje, Alberto Coelho, Abdelaziz El Maatougui, José Manuel Blanco, and Eddy Sotelo
  ACS Combinatorial Science2011 13 (1), 89-95

  • Supported p-Toluenesulfonic Acid as a Highly Robust and Eco-Friendly Isocyanide Scavenger

    Jhonny Azuaje, Alberto Coelho, Abdelaziz El Maatougui, José Manuel Blanco, and Eddy Sotelo
    ACS Combinatorial Science2011 13 (1), 89-95

    We document here the use of polymer-supported p-toluenesulfonic acid as a highly effective, robust, economical and eco-friendly isocyanide scavenger. The herein described strategy circumvent the intense and repulsive odor of volatile isocyanides, enabling ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  O-Silylative Passerini Reaction: A New One-Pot Synthesis of α-Siloxyamides

  Takahiro Soeta, Yuuki Kojima, Yutaka Ukaji, and Katsuhiko Inomata
  Organic Letters2010 12 (19), 4341-4343

  • O-Silylative Passerini Reaction: A New One-Pot Synthesis of α-Siloxyamides

    Takahiro Soeta, Yuuki Kojima, Yutaka Ukaji, and Katsuhiko Inomata
    Organic Letters2010 12 (19), 4341-4343

    A new method for the highly effective synthesis of α-siloxyamides is described. The addition of isocyanide to aldehyde proceeded smoothly in the presence of silanol to give the corresponding α-siloxyamides in high yields. A wide range of aldehydes and ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Palladium-Catalyzed Cyclocoupling of 2-Halobiaryls with Isocyanides via the Cleavage of Carbon−Hydrogen Bonds

  Mamoru Tobisu, Shinya Imoto, Sana Ito and Naoto Chatani
  The Journal of Organic Chemistry2010 75 (14), 4835-4840

  • Palladium-Catalyzed Cyclocoupling of 2-Halobiaryls with Isocyanides via the Cleavage of Carbon−Hydrogen Bonds

    Mamoru Tobisu, Shinya Imoto, Sana Ito and Naoto Chatani
    The Journal of Organic Chemistry2010 75 (14), 4835-4840

    To demonstrate the utility of isocyanides in catalytic C−H bond functionalization reactions, a palladium-catalyzed cyclocoupling reaction of 2-halobiaryls with isocyanides was developed. The reaction afforded an array of fluorenone imine derivatives via ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Synthesis of 2-Boryl- and Silylindoles by Copper-Catalyzed Borylative and Silylative Cyclization of 2-Alkenylaryl Isocyanides

  Mamoru Tobisu, Hirokazu Fujihara, Keika Koh and Naoto Chatani
  The Journal of Organic Chemistry2010 75 (14), 4841-4847

  • Synthesis of 2-Boryl- and Silylindoles by Copper-Catalyzed Borylative and Silylative Cyclization of 2-Alkenylaryl Isocyanides

    Mamoru Tobisu, Hirokazu Fujihara, Keika Koh and Naoto Chatani
    The Journal of Organic Chemistry2010 75 (14), 4841-4847

    We have developed a method for the synthesis of 2-borylindoles via the copper(I)-catalyzed borylative cyclization of 2-alkenylphenyl isocyanides using diboronate. The reaction proceeds at room temperature under neutral conditions and exhibits high ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links

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