Issue 6, 2011

Naphthaleneproton sponges as hydride donors: diverse appearances of the tert-amino-effect

Abstract

It has been shown that the 1-NMe2 group in the 2-substituted 1,8-bis(dimethylamino)naphthalenes (proton sponges) can intramolecularly donate a hydride ion to an appropriate electron-accepting ortho-substituent such as diarylcarbenium ion, β,β′-dicyanovinyl or methyleneiminium group. This produces the 1-N+(Me)[double bond, length as m-dash]CH2 functionality and triggers a number of further transformations (tert-amino effect) including peri-cyclization, ortho-cyclization or hydrolytic demethylation. In each particular case, the course of the reaction is determined by the nature of the ortho-substituent and the most potent nucleophile presenting in the reaction mixture. For 2,7-disubstituted 1,8-bis(dimethylamino)naphthalenes, two types of tandem tert-amino effect with the involvement of both peri-NMe2 groups have been registered. The conclusion was made that proton sponges are generally more active in the tert-amino reactions than the corresponding monodimethylaminoarenes. This is ascribed both to higher electron donor ability of proton sponges and markedly shortened distance between electrophilic Cα-atom in the ortho-substituent and hydrogen atoms of the nearest NMe2 group. Most conversions observed proceed in good to high yields and are useful for the preparation of derivatives of benzo[h]quinoline, quino[7,8:7′,8′]quinoline, 2,3-dihydroperimidine, N,N,N′-trimethyl-1,8-diaminonaphthalene and proton sponge itself.

Graphical abstract: Naphthalene proton sponges as hydride donors: diverse appearances of the tert-amino-effect

Supplementary files

Article information

Article type
Paper
Submitted
18 Oct 2010
Accepted
13 Dec 2010
First published
15 Dec 2010

Org. Biomol. Chem., 2011,9, 1887-1900

Naphthalene proton sponges as hydride donors: diverse appearances of the tert-amino-effect

A. F. Pozharskii, M. A. Povalyakhina, A. V. Degtyarev, O. V. Ryabtsova, V. A. Ozeryanskii, O. V. Dyablo, A. V. Tkachuk, O. N. Kazheva, A. N. Chekhlov and O. A. Dyachenko, Org. Biomol. Chem., 2011, 9, 1887 DOI: 10.1039/C0OB00899K

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