Nitrile ylide dimerization: investigation of the carbene reactivity of nitrile ylides

The Journal of Organic Chemistry
Suzanne FergusAnthony F Hegarty

Abstract

A series of novel hexaaryl diazatrienes 5 ("nitrile ylide dimers") were synthesized directly from the corresponding diaryl ketimines 12 and dichlorotoluenes 13 in a facile one-pot synthesis. The carbene character of the nitrile ylides was investigated by varying the substituents on the aromatic ring adjacent to the carbene center. The isolation of the corresponding carbene dimers as stable crystalline materials with absorption maxima (lambda(max)) from 363 to 422 nm was shown to be promoted by the absence of strongly electron-withdrawing substituents. The crystal structures indicate that the E-isomers were isolated when phenyl, 3-methylphenyl, and 3-chlorophenyl substituents are present at the carbene carbon; the Z-isomer was isolated when the more sterically hindered 2,4,6-trimethylphenyl substituent (Mes) is present. The (1)H NMR spectra of the E-isomers demonstrate the nonequivalence of the aromatic rings, in which two of the aromatic rings of the imine moiety are pseudoaxial and the remaining aromatic rings are pseudoequatorial. The reactions proceed via the intermediate nitrile ylides 1 generated by the base-promoted 1,1-elimination of HCl from the intermediate chloroimine 14. The nitrile ylide was also generated by 1,3-el...Continue Reading

References

Feb 1, 2003·The Journal of Organic Chemistry·Xavier CattoënGuy Bertrand
Jan 8, 2004·Journal of the American Chemical Society·Alexander MaltsevCurt Wentrup
Jan 30, 2004·Journal of the American Chemical Society·Michael OttoGuy Bertrand
Sep 17, 2004·Journal of the American Chemical Society·Pawel Bednarek, Curt Wentrup

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Citations

Sep 25, 2010·Chemical Communications : Chem Comm·Reyna K V Lim, Qing Lin
Jun 5, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Edwin W Y Wong, David J H Emslie
Sep 4, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·I SteciukK Woźniak
Jul 26, 2013·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Omar KhoumeriPatrice Vanelle
Jan 26, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Sara DolciStefano Zacchini
May 14, 2014·The Journal of Organic Chemistry·Guido V JanssenRomano V A Orru
Jul 28, 2020·Organic Letters·Babasaheb Sopan GoreJeh-Jeng Wang
Apr 26, 2019·The Journal of Organic Chemistry·Yuuka HiroseTomohiro Maegawa

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