Synthesis 2006(21): 3547-3574  
DOI: 10.1055/s-2006-950290
PAPER
© Georg Thieme Verlag Stuttgart · New York

Cobalt-Catalyzed Cross-Coupling Reactions of Heterocyclic Chlorides with Arylmagnesium Halides and of Polyfunctionalized Arylcopper Reagents with Aryl Bromides, Chlorides, Fluorides and Tosylates

Tobias J. Korn, Matthias A. Schade, Murthy N. Cheemala, Stefan Wirth, Simon A. Guevara, Gérard Cahiez, Paul Knochel*
Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5-13, 81377 München, Germany
Fax: +49(89)218077680; e-Mail: paul.knochel@cup.uni-muenchen.de;
Further Information

Publication History

Received 25 April 2006
Publication Date:
12 October 2006 (online)

Abstract

A range of aromatic organocopper or organomagnesium compounds undergo smooth cross-coupling reactions with aryl bromides, chlorides, fluorides and tosylates, leading to polyfunctionalized aromatics or heterocycles in the presence of cobalt salts (5-7.5 mol%) as catalysts. Very mild reaction conditions are needed and, in the case of cross-coupling with organocopper compounds, Bu4NI (1 equiv) and 4-fluorostyrene (20 mol%) are essential as promoters for successful couplings.

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19

In the absence of the cobalt catalyst, full conversion (GC) was detected only after four days at room temperature.

21

Commercial cobalt powder was used (Aldrich, 99.9+% purity).

22

Commercial iron powder was used (Merck, ≥99.5% purity).

25

After 24 hours reaction time only 47% conversion was observed.

28

29% conversion was observed after four hours and 42% conversion after 21 hours reaction time at 80 °C.

29

Besides DMPU, NMP and N,N-dimethylacetamide (DMAC) also led to a rate acceleration, but DMPU showed the strongest effect.

33

Confirmed by HMBC-NMR analysis.

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No full conversion was observed if only 1.7 or 2 equivalents of copper reagent were used. In the absence of the cobalt-catalyst, no product was detected even after two days.

38

A mixture of mono- and two-fold cross-coupling product was obtained if only three equivalents of the arylcopper reagents 5l or 5i was used.