钯催化烯丙醇室温下胺基化新方法
烯丙胺结构广泛存在于天然产物，药物，功能材料和农药中，因此对于烯丙胺的研究有很高的应用价值。现存的很多药物中都含有烯丙胺结构，因此寻找一种高效稳定的合成烯丙胺的方法有着重要的意义。
合成烯丙胺骨架的最高效的方法就是在过渡金属进行催化下由烯丙醇直接得到烯丙胺。1999年， Yang 和Moritani就曾报道了钯催化下烯丙醇和胺制备烯丙胺的方法，但要加入Lewis酸促进羟基的离去性，并要求较高的温度下进行。
Yang, S. -C.; Hung, C.-W. J. Org. Chem. 1999, 64, 5000.
另外一种比较好的方法是利用[Pd(allyl)Cl]2 和 1,7-bis(diphenylphosphino)-1H-indole络合物的催化下，在二氧六环80℃下反应，而且不发生加成等副反应。但是此双膦配体比较少见而且很难合成。
Ghosh, R.; Sarkar, A. J. Org. Chem. 2011, 76, 8508.
Pd(Xantphos)Cl2催化的由烯丙醇制备烯丙胺的方法，只要在室温下就能进行，无加成等副反应，官能团耐受度很高，立体选择性好。
A. Pd(Xantphos)Cl2. An oven-dried, 100-mL Schlenk flask containing a
magnetic stir bar (2.5 x 0.8 cm Teflon-coated) (Note 1) is fitted with a reflux
conderser and connected to a vacuum line via a one-stopcock adapter in the
side arm. The flask is flushed with nitrogen (Note 2) and charged with
Pd(CH3CN)2Cl2 (1.0 g, 3.86 mmol, 1 equiv) (Note 3), Xantphos (2.46 g,
4.24 mmol, 1.1 equiv) (Note 4) and benzene (80 mL) (Note 5). The reaction
mixture is stirred for 48 h at 110 °C (oil bath). After cooling to room
temperature, the yellow solid is collected by filtration. The solid is
successively washed with benzene (3 x 30 mL) and Et2O (3 x 30 mL), then
dried under vacuum (1.0 mmHg) for 5 h to give Pd(Xantphos)Cl2 (2.88 g,
98%) (Note 6) as a yellow solid in 99.2% purity, as determined by
quantitative 1H NMR spectroscopy
B. (E)-N,N-Dibenzyl-3-phenylprop-2-en-1-amine. An oven-dried, 100-mL
Schlenk flask equipped with a magnetic stir bar (2.5 x 0.8 cm Teflon-coated,
ovoid-shaped) is connected to a vacuum line via a one-stopcock adapter in
the side arm. The flask is flushed with nitrogen and charged with
Pd(Xantphos)Cl2 (945 mg, 1.25 mmol, 0.05 equiv) and i-PrOH (30 mL) (Note
8). The reaction mixture is stirred for one min at room temperature,
subsequently (E)-3-phenylprop-2-en-1-ol (3.35 g, 25.0 mmol, 1.0 equiv)
(Note 9) is added via syringe in one portion (Note 10). Then dibenzylamine
(4.8 mL, 25 mmol, 1 equiv) (Note 11) is added via syringe in one portion,
and the reaction mixture is stirred for 19 h at room temperature (Notes
12 and 13). The solvent is concentrated in water-aspirator vacuum at
(30 mmHg, 40 °C) to obtain the crude product as the viscous brown oil. The
resulting residue is purified by column chromatography on silica gel
(Note 14) to furnish 7.1 g (91% yield) of ethyl (E)-3-(2-acetamido-4-
methylphenyl)acrylate as a colorless oil (Notes 15 and 16) with a purity of
98.3%, as determined by quantitative 1H NMR spectroscopy and GC
analysis。
编译自：Org. Synth. 2016, 93, 341-351，DOI: 10.15227/orgsyn.093.0341