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

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.

Key words

cross-coupling - organometallic reagents - bismuth - palladium - hypervalent

References

• 1a Metal-Catalyzed Cross-Coupling Reactions   Diederich F. Stang PJ. Wiley-VCH; Weinheim: 1998. 
• 1b Hassan J. Sevignon M. Gozzi C. Schulz E. Lemaire M. Chem. Rev.  2002,  102:  1359 
• 2 For a recent review, see: Littke AF. Fu GC. Angew. Chem. Int. Ed.  2002,  41:  4176 
• For recent works, see:
• 3a Fürstner A. Leitner A. Angew. Chem. Int. Ed.  2002,  41:  609 
• 3b Gstöttmayer CWK. Böhm VPW. Herdtweck E. Grosche M. Herrmann WA. Angew. Chem. Int. Ed.  2002,  41:  1363 
• 3c Schareina T. Kempe R. Angew. Chem. Int. Ed.  2002,  41:  1521 
• 3d Schnyder A. Indolese AF. Studer M. Blaser H.-U. Angew. Chem. Int. Ed.  2002,  41:  3668 
• 3e Bedford RB. Cazin CSJ. Hazelwood SL. Angew. Chem. Int. Ed.  2002,  41:  4120 
• 3f Grasa GA. Viciu MS. Huang J. Zhang C. Trudell ML. Nolan SP. Organometallics  2002,  21:  2866 
• 3g Fürstner A. Leitner A. Méndez M. Krause H. J. Am. Chem. Soc.  2002,  124:  13856 
• 3h Choudary BM. Madhi S. Chowdari NS. Kantam ML. Sreedhar B. J. Am. Chem. Soc.  2002,  124:  14127 
• 3i Roca FX. Richards CJ. Chem. Commun.  2003,  3002 
• 3j Navarro O. Kelly RA. Nolan SP. J. Am. Chem. Soc.  2003,  125:  16194 
• For reviews on the utilization of organobismuth compounds in organic synthesis, see:
• 4a Suzuki H. Ikegami T. Matano Y. Synthesis  1997,  249 
• 4b Suzuki H. Matano Y. In Chemistry of Arsenic, Antimony and Bismuth   Norman NC. Blackie Academic and Professional; London: 1998.  Chap. 6.
• 4c Elliott GI. Konopelski JP. Tetrahedron  2001,  57:  5683 
• 4d Organobismuth Chemistry   Suzuki H. Matano Y. Elsevier; Amsterdam: 2001. 
• 4e Matano Y. Yuki Gosei Kagaku Kyokaishi  2001,  59:  834 ; Chem. Abstr. 2001, 135, 371248j
• 5a Rao MLN. Shimada S. Tanaka M. Org. Lett.  1999,  1:  1271 
• 5b Rao MLN. Yamazaki O. Shimada S. Tanaka T. Suzuki Y. Tanaka M. Org. Lett.  2001,  3:  4103 
• 5c Rao MLN. Shimada S. Yamazaki O. Tanaka M. J. Organomet. Chem.  2002,  659:  117 
• 5d Shimada S. Yamazaki O. Tanaka T. Rao MLN. Suzuki Y. Tanaka M. Angew. Chem. Int. Ed.  2003,  42:  1845 
• 6a Ohkata K. Takemoto S. Ohnishi M. Akiba K. Tetrahedron Lett.  1989,  30:  4841 
• 6b Minoura M. Kanamori Y. Miyake A. Akiba K. Chem. Lett.  1999,  861 
• 6c Shimada S. Yamazaki O. Tanaka T. Suzuki Y. Tanaka M. J. Organomet. Chem.  2004,  in press 
• 7 Shimada S. Rao MLN. Tanaka M. Organometallics  2000,  19:  931 
• 8a Casey CP. Whiteker GT. Isr. J. Chem.  1990,  30:  299 
• 8b van Leeuwen P. Kamer PCJ. Reek JNH. Dierkes P. Chem. Rev.  2000,  100:  2741 
• For example, see:
• 9a Littke AF. Fu GC. Angew. Chem. Int. Ed.  1998,  37:  3387 
• 9b Littke AF. Fu GC. Angew. Chem. Int. Ed.  1999,  38:  2411 
• 9c Littke AF. Dai CY. Fu GC. J. Am. Chem. Soc.  2000,  122:  4020 
• 11 Fitton P. Rick EA. J. Organomet. Chem.  1971,  28:  287 
• 13a

  Shimada, S.; Tanaka, M. unpublished results.

• 13b

  Oxidative addition of 1 toward Pt(PEt₃)₃ takes place even at -50 °C and is complete within 1 h at 0 °C, while that of 2a toward Pt(PEt₃)₃ is slow at r.t. and is not complete, and seems to reach equilibrium at about 60% conversion.

10

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%).

12

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.