RSS-Feed abonnieren
DOI: 10.1055/s-2007-967975
Ytterbium(III) Triflate Catalyzed [3+2] Cycloaddition of N-Arylimines and Epoxides: A Novel and Solvent-Free Synthesis of Substituted 1,3-Oxazolidines
Publikationsverlauf
Publikationsdatum:
21. Februar 2007 (online)
Abstract
The [3+2] cycloaddition of N-arylimines and epoxides was efficiently catalyzed by ytterbium(III) triflate under solvent-free conditions to afford 1,3-oxazolidines in high yields.
Key words
ytterbium(III) triflate - cycloaddition - 1,3-oxazolidines - N-arylimines - epoxides
-
1a
Agami C.Couty F. Eur. J. Org. Chem. 2004, 677 -
1b
Agami C.Comesse S.Kadouri-Puchot C. J. Org. Chem. 2002, 67: 1496 -
1c
Adam W.Schambony SB. Org. Lett. 2001, 3: 79 -
1d
Iwata A.Tang H.Kunai A.Ohshita J.Yamamoto Y.Matui C. J. Org. Chem. 2002, 67: 5170 -
2a
Monge A.Aldana I.Cerecetto H.Rivero A. J. Heterocycl. Chem. 1995, 32: 1429 -
2b
Moloney GP.Craik DJ.Iskander MN.Nero TL. J. Chem. Soc., Perkin Trans. 2 1998, 199 -
2c
Chung SJ.Chung S.Lee HS.Kim EJ.Oh KS.Chol HS.Kim KS.Kim YJ.Hahn JH.Kim D. J. Org. Chem. 2001, 66: 6462 -
3a
Allin SM.Hodkinson CC.Taj N. Synlett 1996, 781 -
3b
Yli-Kauhaluoma JT.Harwig CW.Wentworth JP. Tetrahedron Lett. 1998, 39: 2269 -
4a
Nishitani T.Shiraishi H.Sakaguchi S.Ishii Y. Tetrahedron Lett. 2000, 41: 3389 -
4b
Huo CD.Wei R.Zhang W.Yang L.Liu ZL. Synlett 2005, 161 -
5a
Curini M.Epifano F.Marcotullio MC.Rosati O. Tetrahedron Lett. 2001, 42: 3193 -
5b
Li JJ.Su WK.Lin JD.Chen M.Li J. Synth. Commun. 2005, 35: 1929 -
5c
Curini M.Epifano F.Maltese F.Rosati O. Tetrahedron Lett. 2002, 43: 4895 -
6a
Su WK.Li JJ.Zheng ZG.Shen YC. Tetrahedron Lett. 2005, 46: 6037 -
6b
Su WK.Hong Z.Shan WG.Zhang XX. Eur. J. Org. Chem. 2006, 2723 -
6c
Chen JX.Wu HY.Zheng ZG.Jin C.Zhang XX.Su WK. Tetrahedron Lett. 2006, 47: 5383 - 8
Bulatova OF.Chalova OB.Rakhmankulov DL. Russ. J. Org. Chem. 2001, 37: 1753 - 9 It has been reported that in the 1H NMR data for the cis configuration of 3a and 3d, the proton in the 2-position appeared at δ = 5.85 and δ = 5.84 ppm, respectively; see:
Bulatova OF.Chalova OB.Rakhmankulov DL. Russ. J. Org. Chem. 2001, 37: 1753 - 11
Bynatoba OQ.Pomahob HA. Zh. Org. Khim. 1997, 16: 3658 -
13a
Larksarp C.Alper H. J. Am. Chem. Soc. 1997, 119: 3709 -
13b
Larksarp C.Alper H. J. Org. Chem. 1998, 63: 6229 -
13c
Takaya H.Mashima K.Koyano K.Yagi M.Kumobayashi H.Taketomi T.Akutagawa S.Noyori R. J. Org. Chem. 1986, 51: 629 -
13d
Miyashita A.Yasuda A.Takay H.Toriumi K.Ito T.Souchi Y.Noyori R. J. Am. Chem. Soc. 1980, 102: 7932
References and Notes
5-Chloromethyl-2,3-diphenyloxazolidine (
3a): MS (EI): m/z (%) = 273 (100), 196 (84), 132 (67); IR (film): 1297, 1207, 1109 cm-
1; 1H NMR (400 MHz, CDCl3):
δ (cis-3a) = 7.48-7.36 (m, 5 H), 7.16 (t, J = 7.6 Hz, 2 H), 6.75 (t, J = 7.6 Hz, 1 H), 6.52 (d, J = 7.6 Hz, 2 H), 5.87 (s, 1 H), 4.59-4.50 (m, 1 H), 3.96 (dd, J = 6.0, 8.4 Hz, 1 H), 3.85-3.59 (m, 2 H), 3.51 (dd, J = 8.4, 8.4 Hz, 1 H); 13C NMR (100 MHz, CDCl3-TMS): δ (cis-3a) = 145.4, 139.3, 129.1, 128.9, 128.8, 127.1, 118.2, 113.9, 92.9, 76.7, 52.2, 44.6; 1H NMR (400 MHz, CDCl3): δ (trans-3a) = 7.48-7.36 (m, 5 H), 7.16 (t, J = 7.6 Hz, 2 H), 6.75 (t, J = 7.6 Hz, 1 H), 6.52 (d, J = 7.6 Hz, 2 H), 6.01 (s, 1 H), 4.59-4.50 (m, 1 H), 3.98 (dd, J = 6.0, 8.4 Hz, 1 H), 3.85-3.59 (m, 2 H), 3.51 (dd, J = 8.4, 8.4 Hz, 1 H); 13C NMR (100 MHz, CDCl3-TMS): δ (trans-3a) = 145.2, 139.5, 129.1, 129.0, 128.7, 126.8, 117.9, 113.0, 92.4, 75.2, 51.2, 44.2; Anal. Calcd for C16H16ClNO: C, 70.20; H, 5.89; N, 5.12. Found: C, 70.22; H, 5.90; N, 5.10.
5-Chloromethyl-2,2-diphenyl-3-
p
-tolyloxazolidine (
3i): yellow crystals; mp 125-128 °C; MS (EI): m/z (%) = 363 (22), 286 (64), 146 (100); IR (film): 1322, 1200, 1106 cm-
1; 1H NMR (400 MHz, CDCl3): δ = 7.50-7.24 (m, 10 H), 6.81 (d, J = 8.0 Hz, 2 H), 6.37 (d, J = 8.0 Hz, 2 H), 4.40-4.34 (m, 1 H), 3.84-3.67 (m, 4 H), 2.15 (s, 3 H); 13C NMR (100 MHz, CDCl3-TMS): δ = 142.4, 141.2, 140.5, 129.2, 129.0, 128.8, 128.5, 128.3, 127.9, 126.8, 114.8, 99.7, 74.1, 52.0, 44.7, 20.2; Anal. Calcd for C23H22ClNO: C, 75.92; H, 6.09; N, 3.85. Found: C, 75.90; H, 6.10; N, 3.84.
A mixture of epoxide 1a (0.28 g, 3 mmol), N-arylimine 2a (0.36 g, 2 mmol), and Yb(OTf)3 (0.06 g, 5 mol%) was stirred at 40 °C for 8 h. After complete conversion into 3a, as indicated by TLC, the reaction mixture was purified by silica gel column chromatography using PE-EtOAc (10:1) as eluent to afford the pure product 5-chloromethyl-2,3-diphenyloxazolidine (3a, 0.46 g, 85%, Table [2] ).
12HPLC conditions: Chiracel OD 4.6 × 250mm, hexane-
i-PrOH (85:15), 25 °C.