烯丙胺結構廣泛存在于天然產(chǎn)物，藥物，功能材料和農(nóng)藥中，因此對于烯丙胺的研究有很高的應用價值。現(xiàn)存的很多藥物中都含有烯丙胺結構，因此尋找一種高效穩(wěn)定的合成烯丙胺的方法有著重要的意義。
合成烯丙胺骨架的最高效的方法就是在過渡金屬進行催化下由烯丙醇直接得到烯丙胺。1999年， Yang 和Moritani就曾報道了鈀催化下烯丙醇和胺制備烯丙胺的方法，但要加入Lewis酸促進羥基的離去性，并要求較高的溫度下進行。
Yang, S. -C.; Hung, C.-W. J. Org. Chem. 1999, 64, 5000.
另外一種比較好的方法是利用[Pd(allyl)Cl]2 和 1,7-bis(diphenylphosphino)-1H-indole絡合物的催化下，在二氧六環(huán)80℃下反應，而且不發(fā)生加成等副反應。但是此雙膦配體比較少見而且很難合成。
Ghosh, R.; Sarkar, A. J. Org. Chem. 2011, 76, 8508.
Pd(Xantphos)Cl2催化的由烯丙醇制備烯丙胺的方法，只要在室溫下就能進行，無加成等副反應，官能團耐受度很高，立體選擇性好。
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。
編譯自：Org. Synth. 2016, 93, 341-351，DOI: 10.15227/orgsyn.093.0341
