Prev. Article Next Article Table of Contents

Article

Dicationic Electrophiles from Olefinic Amines in Superacid

Supporting Info

Yun Zhang, Aaron McElrea, Gregorio V. Sanchez, Jr., Dat Do, Alma Gomez, Sharon L. Aguirre,^† Rendy Rendy, and Douglas A. Klumpp*^§

Department of Chemistry, California State Polytechnic University, 3801 West Temple Avenue, Pomona, California 91768

J. Org. Chem., 2003, 68 (13), pp 5119–5122

DOI: 10.1021/jo030024z

Publication Date (Web): May 30, 2003

Dedicated to Professor George A. Olah on the occasion of his 75th birthday.

†

American Chemical Society Scholar, 2001−2002.

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

Present address: Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115.

, daklumpp@csupomona.edu

Abstract

This paper describes the superacid-catalyzed chemistry of olefinic amines and related compounds. A variety of olefinic amines are found to react with benzene in CF₃SO₃H (triflic acid) to give addition products in good yields (75−99%), including the pharmaceutical agents fenpiprane and prozapine. A general mechanism is proposed that invokes the formation of reactive, dicationic electrophiles and the direct observation of a diprotonated species is reported from low-temperature NMR experiments. This chemistry is also used to conveniently prepare functionalized polystyrene beads having pendant amine groups.

View: Full Text HTML | Hi-Res PDF

Tools

SciFinder Links

History

Published In Issue June 27, 2003
Received January 17, 2003

Recommend & Share

Related Content

Reactions of Amino Alcohols in Superacid: The Direct Observation of Dicationic Intermediates and Their Application in SynthesisOrganic Letters
- Reactions of Amino Alcohols in Superacid: The Direct Observation of Dicationic Intermediates and Their Application in Synthesis
  Douglas A. Klumpp, Sharon L. Aguirre, Gregorio V. Sanchez, Jr., and Sarah J. de Leon
  Organic Letters 2001 3 (17), pp 2781–2784
  Abstract: The chemistry of amino alcohols has been studied in superacidic media, and these compounds have been found to ionize cleanly to the dication intermediates. Several dicationic species have been directly observed by low-temperature ¹³C NMR, including those ...
  Abstract | Full Text HTML | Hi-Res PDF
Superacid-Catalyzed Reactions of Cinnamic Acids and the Role of Superelectrophiles¹The Journal of Organic Chemistry
- Superacid-Catalyzed Reactions of Cinnamic Acids and the Role of Superelectrophiles¹
  Rendy Rendy, Yun Zhang, Aaron McElrea, Alma Gomez, and Douglas A. Klumpp
  The Journal of Organic Chemistry 2004 69 (7), pp 2340–2347
  Abstract: The chemistry of cinnamic acids and related compounds has been studied. In superacid-catalyzed reactions with arenes, two competing reaction mechanisms are proposed. Both mechanisms involve the formation of dicationic intermediates (superelectrophiles), ...
  Abstract | Full Text HTML | Hi-Res PDF
Chemistry of Dicationic Electrophiles: Superacid-Catalyzed Reactions of Amino AcetalsThe Journal of Organic Chemistry
- Chemistry of Dicationic Electrophiles: Superacid-Catalyzed Reactions of Amino Acetals
  Douglas A. Klumpp, Gregorio V. Sanchez, Jr., Sharon L. Aguirre, Yun Zhang, and Sarah de Leon
  The Journal of Organic Chemistry 2002 67 (14), pp 5028–5031
  Abstract: Amino acetals are shown to form highly electrophilic systems in Bronsted superacids. It is proposed that amino acetals give dicationic electrophiles, and this proposal is supported by the direct observation of a dication by low-temperature ¹³C NMR. When ...
  Abstract | Full Text HTML | Hi-Res PDF

Article

Dicationic Electrophiles from Olefinic Amines in Superacid