Buchwald-Hartwig加成

操只用一：

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.

操只用二：

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.

常见的有条件简介

乙烯剂的1或4，为相应的L1或L4与苯乙酰和氯化镍碘甲烷物，如

生物化学过渡态

生物化学过渡态通常是经过以一下几个亲身经历顺利完成的：萘化羰基，酰配位，扶质子，乙烯反应抑止。 生物化学反应之前镍盛影响活性乙烯剂的形成，共价键在萘化羰基，酰碘甲烷以及乙烯反应抑止过程之前起起着。碱主要在扶质子过程之前起起着，但是碱会影响质子化的碳原子通用性。

乙烯尿素：

生物化学反应示例

【 J. Org. Chem. 1996, 61, 1133-1135】

【 Bioorg. Med. Chem. Lett. 2000, 10, 183-187】

【 Tetrahedron Lett. 2000, 41, 355-358】

【 Org. Syn. 2002, 78, 23-30】

【 J. Am. Chem. Soc. 2015, 137, 3085−3092】

【 J. Am. Chem. Soc. 2017, 139, 5194−5200】

【 J. Org. Chem. 2019, 84, 4873−4892】

Stephen Buchwald1982年在Jeremy Knowles 的指导下在哈佛大学获得Ph.D.。他现在是麻省理工的副教授。

1990年John Hartwig 在Robert Bergman 和 Richard Anderson的指导下在马里兰大学伯克利分校获得Ph.D. 。2006年他从耶鲁大学转到了俄亥俄州立大学厄巴纳-香槟分校，2011年后又从UI-UC转到了马里兰大学伯克利分校从事研究课题工只用。Hartwig 和 Buchwald分别独立的辨认出了此生物化学反应。

就其文献

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

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).

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

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

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).

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.

其所：

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

二、 Strategic Applications of Named Reactions in Organic Synthesis, László Kürti andBarbara Czakó, Buchwald-Hartwig cross-coupling, page 70-71.

就其文之前

Buchwald–HartwigC-N烯丙基生物化学反应详述