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Synlett 2009(3): 421-424  
DOI: 10.1055/s-0028-1087543
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

α-Arylation of Cyclic Amines by Aryl Transfer in Lithiated Ureas

Renaud Bach, Jonathan Clayden*, Ulrich Hennecke
School of Chemistry, University of Manchester, Oxford Rd., Manchester M13 9PL, UK
Fax: +44(161)2754939; e-Mail: clayden@man.ac.uk;
Further Information

Publication History

Received 22 October 2008
Publication Date:
21 January 2009 (online)

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Abstract

Treatment with base of N′-aryl urea derivatives of het-e­ro- or carbocyclic amines with benzylic nitrogen atoms promotes rearrangement with transfer of the aryl ring from N to C, giving rise to α-arylated products.

Key words

arylation - amines - heterocycles - lithiation - ureas

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8

Alongside remaining starting material, byproducts from this reaction included those arising from ortholithiation of the aryl ring followed by anionic ortho-Fries rearrangement (see Sibi, M. P.; Snieckus, V. J. Org. Chem. 1983, 48, 1935). Quenching the reaction mixture with TMSCl yielded no products of silylation α to nitrogen.

10

The X-ray crystallographic data for 9d has been deposited with the Cambridge Crystallographic Database, deposition number 706267.

12

In THF, decomposition products suggest that lithiation is followed by intra- and/or intermolecular addition to the 2- or 4-position of the pyridyl ring, rather than the 3-position.

13

Compound 19e was made by standard methods from commercially available material.