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Synlett 2009(20): 3287-3290  
DOI: 10.1055/s-0029-1218354
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Organocatalytic Synthesis of Terminal Propargylamine Derivatives by Tandem Amination-Alkynylation

Yu Wang, Fangzhi Peng, Hongbin Zhang, Zhihui Shao*
Key Laboratory of Medicinal Chemistry for Natural Resource (Yunnan University), Ministry of Education, School of Chemical Science and Technology, Yunnan University, Kunming 650091, P. R. of China
e-Mail: +86(871)5035538; e-Mail: 20070114@ynu.edu.cn; e-Mail: zhihui_shao@hotmail.com;
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Publikationsverlauf

Received 7 August 2009
Publikationsdatum:
13. November 2009 (online)

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Abstract

The first organocatalytic synthesis of terminal propargylic amines from aldehydes via tandem amination/Seyferth-­Gilbert alkynylation has been developed. The described protocol provides the formal addition products of acetylene (HC≡CH) to ali­phatic imines, which are not easily obtained directly.

Key words

amination - organocatalysis - Seyferth-Gilbert alkynylation - tandem reactions - terminal propargylamines

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14

Typical procedure for one-pot, tandem α-amination-alkynylation of aldehydes: Proline (0.1 mmol, 10 mol%) was added to a stirring solution of aldehyde 1a (1 mmol) and DIAD (1 mmol) in CH2Cl2 (3 mL). After 2 h of vigorous stirring at r.t., MeOH (15 mL), Ohira-Bestmann reagent (1.2 mmol, 1.2 equiv) and K2CO3 (2 mmol, 2 equiv) were added. After stirring for 12 h at r.t., the reaction mixture was diluted with Et2O. The excess solvents were removed under reduced pressure and the residue was purified by flash silica gel chromatography to give the desired product 2a. IR (film): 3254, 2985, 1743, 1678, 1529, 1417, 1233, 1109 cm-¹; ¹H NMR (300 MHz, CDCl3): δ = 6.39 (br s, 1 H), 5.06 (br s, 1 H), 4.89 (sept, J = 6.2 Hz, 2 H), 2.23 (s, 1 H), 1.36 (d, J = 6.9 Hz, 3 H), 1.18 (d, J = 6.1 Hz, 12 H); ¹³C NMR (75 MHz, CDCl3): δ = 156.1, 154.7, 82.1, 71.5, 70.6, 69.8, 45.8, 22.0, 21.9, 19.2; HRMS (ESI): m/z [M + H]+ calcd for C12H20N2O4: 257.1496; found: 257.1490.