Synlett 2004(11): 1921-1924  
DOI: 10.1055/s-2004-831298
LETTER
© Georg Thieme Verlag Stuttgart · New York

Palladium-Catalyzed Cross-Coupling Reaction of Organobismuth Compounds with Aryl and Alkenyl Chlorides

Osamu Yamazakia, Toshifumi Tanakab, Shigeru Shimada*a, Yohichi Suzukib, Masato Tanaka*a,c
a National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8565, Japan
b Department of Industrial Chemistry, College of Industrial Technology, Nihon University, Narashino, Chiba 275-8575, Japan
c Chemical Resources Laboratory, Tokyo Institute of Technology, Nagatsuta, Midori-ku, Yokohama 226-8503, Japan
Fax: +81(29)8614511; e-Mail: s-shimada@aist.go.jp;
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Publikationsverlauf

Received 8 June 2004
Publikationsdatum:
06. August 2004 (online)

Abstract

Cross-coupling reactions of hypervalent organobismuth compounds, 6-tert-butyl-5,6,7,12-tetrahydrodibenz[c,f][1,5]azabismocines, with aryl and alkenyl chlorides are efficiently catalyzed by the Pd(OAc)2/dppf [dppf = 1,1′-bis(diphenylphosphino)ferrocene] system.

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Typical Procedure: A mixture of 2a (161 mg, 0.30 mmol), 4-CF3C6H4Cl (46 mg, 0.25 mmol), Pd(OAc)2 (5.6 mg, 0.025 mmol) and dppf (14 mg, 0.025 mmol) in 3 mL of NMP was heated at 100 °C for 12 h under N2. The crude mixture was dissolved in EtOAc (90 mL) and washed with aq HCl (4 M, 3 × 10 mL) and H2O (10 mL). The organic layer was dried over Na2SO4, filtered, and concentrated in vacuo. The residue was separated with a short pad of silica gel, eluting with EtOAc-hexane (1:10) to give a mixture containing cross-coupled product and then with CH2Cl2-EtOAc (1:1) to give pure 2e (145 mg, 98%). The former mixture was further purified with PTLC to give 4-trifluoromethylbiphenyl (45 mg, 79%).

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The 31P NMR spectrum of each of the mixture at r.t. showed a broad signal suggesting a rapid exchange of coordinated and uncoordinated PPh3. The signals shifted upfield gradually and reached that of free PPh3 after complete decomposition.