Abstract
The stereoselective addition of phenyl acetylene to imines, catalysed by chiral bis-amine-Cu(I) complexes was studied. The chiral ligands are either commercially available or easily prepared in one or two steps. This very convenient and extremely simple experimental procedure at room temperature allowed optically active propargyl amines to be obtained in good yields with enantioselectivities up to 70%.
Key words
chiral bis-amines - copper complexes - propargylamines - enantioselective catalysis - acetylene addition
References
1a Konishi M.
Ohkuma H.
Tsuno T.
Oki T.
VanDuyne G.
Clardy J.
J. Am. Chem. Soc.
1990,
112:
3715
1b Huffman MA.
Yasuda N.
DeCamp AE.
Grabowski EJ.
J. Org. Chem.
1995,
6:
1590
2a Nilsson B.
Vargas HM.
Ringdahl B.
Hacksell U.
J. Med. Chem.
1992,
35:
285
2b Miura M.
Enna M.
Okuro K.
Nomura M.
J. Org. Chem.
1995,
60:
4999
3 Blanchet J.
Bonin M.
Micouin L.
Org. Prep. Proced. Int.
2002,
34:
459
4a Bloch R.
Chem. Rev.
1998,
98:
1407
4b Enders D.
Reinhold U.
Tetrahedron: Asymmetry
1997,
8:
1895
4c Frantz DE.
Fassler R.
Oetiker J.
Carreira EM.
Angew. Chem. Int. Ed.
2002,
41:
3054
4d Frantz DE.
Fassler R.
Carreira EM.
J. Am. Chem. Soc.
1999,
121:
11245 ; and references cited therein
5a Fischer C.
Carreira EM.
Org. Lett.
2001,
3:
4319
5b Fischer C.
Carreira EM.
Org. Lett.
2004,
6:
1497
5c Wei C.
Li Z.
Li CJ.
Org. Lett.
2003,
5:
4473
6a Cozzi PG.
Hilgraf R.
Zimmermann N.
Eur. J. Org. Chem.
2004,
4095
6b Pu L.
Yu HB.
Chem. Rev.
2001,
101:
757
6c Frantz DE.
Fassler R.
Tomooka CS.
Carreira EM.
Acc. Chem. Res.
2000,
33:
373
7a Traverse JF.
Hoveyda AH.
Snapper ML.
Org. Lett.
2003,
5:
3273
7b Akullian LC.
Hoveyda AH.
Snapper ML.
Angew. Chem. Int. Ed.
2003,
42:
4244
8 Wie C.
Li CJ.
J. Am. Chem. Soc.
2002,
124:
5638
9a Koradin C.
Polborn K.
Knochel P.
Angew. Chem. Int. Ed.
2002,
41:
2535
9b Gommermann N.
Koradin C.
Polborn K.
Knochel P.
Angew. Chem. Int. Ed.
2003,
42:
5763
10 Wei C.
Li Z.
Li C.-J.
Synlett
2004,
1472
11 Knopfel TF.
Aschwanden P.
Ichikawa T.
Watanabe T.
Carreira EM.
Angew. Chem. Int. Ed.
2004,
43:
5971
12 Jiang B.
Si Y.-G.
Angew. Chem. Int. Ed.
2004,
43:
216
13 Benaglia M.
Negri D.
Dell’Anna G.
Tetrahedron Lett.
2004,
45:
8705
14 Puglisi A.
Benaglia M.
Annunziata R.
Bologna A.
Tetrahedron Lett.
2003,
44:
2947
15a Corey EJ.
DaSilva Jardine P.
Virgil S.
Yuen P.-W.
Connell RD.
J. Am. Chem. Soc.
1989,
111:
9243
15b Mimoun H.
Yves de Saint Laumer J.
Giannini L.
Scopelliti R.
Floriani C.
J. Am. Chem. Soc.
1999,
121:
6158
15c Kobayashi S.
Hamada T.
Manabe K.
J. Am. Chem. Soc.
2002,
124:
5640
15d Hamada T.
Manabe K.
Kobayashi S.
J. Am. Chem. Soc.
2004,
126:
7768
16 (1R ,2R )-1,2-trans- Diaminocyclohexane and (1R ,2R )-1,2-diaminodiphenylethylenediamine were also tested as chiral ligands, but with modest results.
17 For reactions promoted by chiral diamine complexes in aqueous solvents, see ref. 15c and 15d.
18 The reaction also worked in MeCN-H2 O, 9:1 (51% yield, 18% ee).
19 Krebs FC.
Jorgensen M.
J. Org. Chem.
2002,
67:
7511
20 Miyano S.
Nawa M.
Mori A.
Hashimoto H.
Bull. Chem. Soc. Jpn.
1984,
2171
21
N- Benzyl- and N -alkylimines did not react under our reaction conditions.
