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Synthesis 2009(4): 681-686  
DOI: 10.1055/s-0028-1083286
PSP
© Georg Thieme Verlag Stuttgart ˙ New York

Palladium-Catalyzed Cross-Couplings of Unsaturated Halides Bearing Relatively Acidic Hydrogen Atoms with Organozinc Reagents

Zhibing Donga,b, Georg Manolikakesa, Jinshan Lib, Paul Knochel*a
a Department Chemie und Biochemie, Ludwig-Maximilians-Universität München, Butenandtstraße 5-13, Haus F, 81377 München, Germany
Fax: +49(89)218077680; e-Mail: paul.knochel@cup.uni-muenchen.de;
b State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, P. R. of China
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Publication History

Received 4 August 2008
Publication Date:
19 December 2008 (online)

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Abstract

A wide range of polyfunctional aryl, heteroaryl, alkyl, and benzylic zinc reagents were coupled with unsaturated aryl halides bearing an acidic NH or OH proton, using palladium(II) acetate (1 mol%), and S-Phos (2 mol%) as catalyst without the need of protecting groups.

Key words

palladium catalysis - cross-coupling - functionalized zinc reagents - polyfunctional biaryls

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Typical pK a values (in DMSO) for anilines range between 20-30; for a comprehensive compilation of pK a data see http://www.chem.wisc.edu/areas/reich/pkatable/index.htm and references cited therein.

12

Our experiments indicate a relative kinetic basicity of zinc reagents: arylzinc halide > alkylzinc halide > benzylic zinc halide. For further experimental details, see ref. 7.