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Article

Thermodynamic Stability and Reactivity of Silylated Bis(oxy)iminium Ions

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Yulia A. Khomutova,^† Vladimir O. Smirnov,^† Herbert Mayr,^‡ and Sema L. Ioffe*^†

N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospekt 47, 119991 Moscow, Russian Federation, and Department Chemie und Biochemie, Ludwig-Maximilians-Universtt Mnchen, Butenandtstrasse 5-13 (Haus F), 81377 Mnchen, Germany

J. Org. Chem., 2007, 72 (24), pp 9134–9140

DOI: 10.1021/jo070633x

Publication Date (Web): October 31, 2007

†

Russian Academy of Sciences.

‡

Ludwig-Maximilians-Universtät München.

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

, iof@ioc.ac.ru

Abstract

Silylation of various nitronates with trialkylsilyl triflates was investigated by applying NMR techniques. In several cases, a flexible nitronate−bis(oxy)iminium ion (as an ion pair with triflate as counterion) equlibrium was found, and its thermodynamic parameters were determined. Elevation of temperature or dilution shifts this equilibrium toward the reactants. Activation parameters for the C,C-coupling reaction of silylated bis(oxy)iminium ions with a series of reference nucleophiles were determined. Estimated electrophilicity of bis(oxy)iminium ions allows one to count on C,C-coupling when partner nucleophilicity is N > 4.

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Published In Issue November 23, 2007
Received April 13, 2007

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Article

Thermodynamic Stability and Reactivity of Silylated Bis(oxy)iminium Ions

Abstract

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Recommend & Share

Related Content

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Nickel-Catalyzed [4 + 2] Cycloaddition of Enones with Alkynes

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