TMS2NCa類催化劑存在下，胺加成到烯烴上得到氫胺化產(chǎn)物的反應(yīng)。ω-氨基烯烴進(jìn)行分子內(nèi)的此反應(yīng)可以到吡咯烷類化物。除了Ca可以催化此反應(yīng)，鑭系金屬也可以很好催化此反應(yīng)，對(duì)于不對(duì)稱催化，效果更好。
反應(yīng)機(jī)理
反應(yīng)實(shí)例
Pyrrolidine (4) (general procedure). Catalyst 2 (2–10 mol %) was added to 200–500 mg of aminoalkene 1 in 5 mL of PhH under Ar and the mixture was stirred until homogeneous. After quenching by exposure to air, rotary evaporation and bulb-to-bulb distillation gave 4, which was treated with HCl in
diethyl ether and analyzed by NMR.
【Hill MS, Barrett AGM, J Am Chem Soc., 2009, 131, 9670】
2-Benzylaminoethylbenzene (7). Styrene 5 (2.5 mmol) and benzylamine 6 (2.5 mmol) were treated under Ar with Ca{N(SiMe3)2}2 and the mixture was heated to 60 C for 48 h (faster reaction with Sr{N(SiMe3)2}2]). After exposure to air and dilution with Et2O, the suspension was filtered through Celite and evaporated to afford 2-benzyl-aminoethylbenzene 7 (oil, 92%), purified by chromatography or vacuum distillation.
【Hill MS, Barrett AGM, J Am Chem Soc., 2009, 131, 12906】
相關(guān)文獻(xiàn)
1 Marks TJ Acc Chem Res 2004 37 673
2 Hill MS J Am Chem Soc 2005 127 2042
3 Hill MS Organometal 2007 26 2953
4 Harder S Z Naturforsch 2008 63b 169
5 Hill MS, Barrett AGM J Am Chem Soc 2009 131 9670
6 Hill MS, Barrett AGM J Am Chem Soc 2009 131 12906
7 Harder S Chem Rev 2010 110 3852
編譯自：Organic Syntheses Based On Name Reactions, 3RdEd, A. Hassner, Page 216-217.
