操作一：

An oven-dried Schlenk tube was charged with cesium carbonate which had been finely ground with a mortar and pestle (1.4 eq) in a nitrogen-filled glovebox. The tube was capped with a rubber septum and removed from the glovebox. The tube was then charged with Pd2(dba)3 or Pd(OAc)2 and BINAP or PPF-OMe, and purged with argon. The aryl bromide (1.0 eq), the amine (1.2 eq), and toluene (2 mL/mmol halide) were added, and the mixture was heated to 100 oC with stirring until the starting material had been consumed as judged by GC analysis. The mixture was cooled to room temperature, diluted with ether (20 ml), filtered, and concentrated. The crude product was then purified by flash chromatography on silica gel.

操作二：

Pd(OAc)2 (0.025 mol%) and P(t-Bu)3 or Xantphose (0.10 mol%)(Phosphine/Pd=4:1) were added to the suspension of aryl halide (40 mmol), diarylamine (40 mmol) and NaOtBu (48 mmol) in o-xylene (60 mL) in N2 atmosphere. The mixture was heated for 3 h at 120 oC. Subsequently, it was cooled to room temeperature. H2O (60 mL) was added to it, the organic layer was separated and concentrated. The crude product was then purified by flash chromatography on silica gel or re-crystallization with MeOH/THF.

常见的条件汇总

催化剂的1或4，为相应的L1或L4与苯乙胺和氯化钯络合物，如

反应机理

催化循环

反应实例

参考文献

1. (a) Paul, F.; Patt, J.; Hartwig, J. F. J. Am. Chem. Soc. 1994, 116, 5969-5970. John Hartwig earned his at the University of California-Berkeley in 1990 under the guidance of Robert Bergman and Richard Anderson. He moved from Yale University to the University of Illinois at Urbana-Champaign in 2006 and moved from UI-UC to UC Berkeley in 2011. Hartwig and Buchwald independently discovered this chemistry. （1990年John Hartwig 在Robert Bergman 和 Richard Anderson的指导下在加州大学伯克利分校获得Ph.D. 。2006年他从耶鲁大学转到了伊利诺伊大学厄巴纳-香槟分校，2011年后又从UI-UC转到了加州大学伯克利分校从事研究工作。Hartwig 和 Buchwald分别独立的发现了此反应。）

(b) Mann, G.; Hartwig, J. F. J. Org. Chem. 1997, 62, 5413-5418. (c) Mann, G.;Hartwig, J. F. Tetrahedron Lett. 1997, 38, 8005-8008.

2. (a) Guram, A. S.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 7901-7902. Stephen Buchwald received his Ph.D. in 1982 under Jeremy Knowles at Harvard University. He is currently a professor at MIT. （Stephen Buchwald1982年在Jeremy Knowles 的指导下在哈佛大学获得Ph.D.。他现在是麻省理工大学的教授。） (b) Palucki, M.; Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. 1996, 118, 10333-10334.

3. Wolfe, J. P.; Buchwald, S. L. J. Org. Chem. 1996, 61, 1133-1135.

4. Driver, M. S.; Hartwig, J. F. J. Am. Chem. Soc. 1996, 118, 7217-7218.

5. Wolfe, J. P.; Wagaw, S.; Marcoux, J.-F.; Buchwald, S. L. Acc. Chem. Res. 1998, 31, 805-818. (Review).

6. Hartwig, J. F. Acc. Chem. Res. 1998, 31, 852-860. (Review).

7. Frost, C. G.; Mendonça, P. J. Chem. Soc., Perkin Trans. 1 1998, 2615-2624. (Review).

8. Yang, B. H.; Buchwald, S. L. J. Organomet. Chem. 1999, 576, 125-146. (Review).

9. Hartwig, J. F.; Kawatsura, M.; Hauck, S. I.; Shaughnessy, K. H.; Alcazar-Roman, L.M. J. Org. Chem. 1999, 64, 5575-5580.

10. Wolfe, J. P.; Buchwald, S. L. Org. Syn. 2002, 78, 23-30.

11. Urgaonkar, S.; Verkade, J. G. J. Org. Chem. 2004, 69, 9135-9142.

12. Csuk, R.; Barthel, A.; Raschke, C. Tetrahedron 2004, 60, 5737-5750.

13. Janey, J. M. Buchwald–Hartwig amination, In Name Reactions for Functional Group Transformations; Li, J. J., Corey, E. J. Eds.; Wiley: Hoboken, NJ, 2007, pp 564-609.(Review).

14. Li, J. J.; Wang, Z.; Mitchell, L. H. J. Org. Chem. 2007, 72, 3606-3607.

15. Lorimer, A. V.; O’Connor, P. D.; Brimble, M. A. Synthesis 2008, 2764-2770.

16. Nodwell, M.; Pereira, A.; Riffell, J. L.; Zimmerman, C.; Patrick, B. O.; Roberge, M.; Andersen, R. J. J. Org. Chem. 2009, 74, 995-1006.

17. Witt, A.; Teodorovic, P.; Linderberg, M.; Johansson, P.; Minidis, A. Org. Process Res.Dev. 2013, 17, 672–678.

18. Raders, S. M.; Moore, J. N.; et al. Org. Chem. 2013, 78, 4649-4664.

编译自：J.J. Li, Name Reactions: A Collection of Detailed Mechanisms and Synthetic Applications,  Buchwald–Hartwig amination，page 91-94.