Ytterbium(III) Triflate Catalyzed [3+2] Cycloaddition of N-Arylimines and Epoxides: A Novel and Solvent-Free Synthesis of Substituted 1,3-Oxazolidines

Chuanming Yu; Xiaoping Dai; Weike Su

doi:10.1055/s-2007-967975

LETTER

Ytterbium(III) Triflate Catalyzed [3+2] Cycloaddition of N-Arylimines and Epoxides: A Novel and Solvent-Free Synthesis of Substituted 1,3-Oxazolidines

Chuanming Yu, Xiaoping Dai, Weike Su*
College of Pharmaceutical Sciences, Zhejiang University of Technology, Zhejiang Key Laboratory of Pharmaceutical Engineering, Hangzhou 310014, P. R. of China
Fax: +86(571)88320752; e-Mail: suweike@zjut.edu.cn;

Abstract

All articles of this category

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

Full Text

References

References and Notes

<A NAME="RW24106ST-1A">1a</A> Agami C. Couty F. Eur. J. Org. Chem. 2004, 677

<A NAME="RW24106ST-1B">1b</A> Agami C. Comesse S. Kadouri-Puchot C. J. Org. Chem. 2002, 67: 1496

<A NAME="RW24106ST-1C">1c</A> Adam W. Schambony SB. Org. Lett. 2001, 3: 79

<A NAME="RW24106ST-1D">1d</A> Iwata A. Tang H. Kunai A. Ohshita J. Yamamoto Y. Matui C. J. Org. Chem. 2002, 67: 5170

<A NAME="RW24106ST-2A">2a</A> Monge A. Aldana I. Cerecetto H. Rivero A. J. Heterocycl. Chem. 1995, 32: 1429

<A NAME="RW24106ST-2B">2b</A> Moloney GP. Craik DJ. Iskander MN. Nero TL. J. Chem. Soc., Perkin Trans. 2 1998, 199

<A NAME="RW24106ST-2C">2c</A> 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

<A NAME="RW24106ST-3A">3a</A> Allin SM. Hodkinson CC. Taj N. Synlett 1996, 781

<A NAME="RW24106ST-3B">3b</A> Yli-Kauhaluoma JT. Harwig CW. Wentworth JP. Tetrahedron Lett. 1998, 39: 2269

<A NAME="RW24106ST-4A">4a</A> Nishitani T. Shiraishi H. Sakaguchi S. Ishii Y. Tetrahedron Lett. 2000, 41: 3389

<A NAME="RW24106ST-4B">4b</A> Huo CD. Wei R. Zhang W. Yang L. Liu ZL. Synlett 2005, 161

<A NAME="RW24106ST-5A">5a</A> Curini M. Epifano F. Marcotullio MC. Rosati O. Tetrahedron Lett. 2001, 42: 3193

<A NAME="RW24106ST-5B">5b</A> Li JJ. Su WK. Lin JD. Chen M. Li J. Synth. Commun. 2005, 35: 1929

<A NAME="RW24106ST-5C">5c</A> Curini M. Epifano F. Maltese F. Rosati O. Tetrahedron Lett. 2002, 43: 4895

<A NAME="RW24106ST-6A">6a</A> Su WK. Li JJ. Zheng ZG. Shen YC. Tetrahedron Lett. 2005, 46: 6037

<A NAME="RW24106ST-6B">6b</A> Su WK. Hong Z. Shan WG. Zhang XX. Eur. J. Org. Chem. 2006, 2723

<A NAME="RW24106ST-6C">6c</A> Chen JX. Wu HY. Zheng ZG. Jin C. Zhang XX. Su WK. Tetrahedron Lett. 2006, 47: 5383

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 NAME="RW24106ST-8">8</A> Bulatova OF. Chalova OB. Rakhmankulov DL. Russ. J. Org. Chem. 2001, 37: 1753

<A NAME="RW24106ST-9">9</A> 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

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] ).

<A NAME="RW24106ST-11">11</A> Bynatoba OQ. Pomahob HA. Zh. Org. Khim. 1997, 16: 3658

HPLC conditions: Chiracel OD 4.6 × 250mm, hexane-
i-PrOH (85:15), 25 °C.

<A NAME="RW24106ST-13A">13a</A> Larksarp C. Alper H. J. Am. Chem. Soc. 1997, 119: 3709

<A NAME="RW24106ST-13B">13b</A> Larksarp C. Alper H. J. Org. Chem. 1998, 63: 6229

<A NAME="RW24106ST-13C">13c</A> Takaya H. Mashima K. Koyano K. Yagi M. Kumobayashi H. Taketomi T. Akutagawa S. Noyori R. J. Org. Chem. 1986, 51: 629

<A NAME="RW24106ST-13D">13d</A> Miyashita A. Yasuda A. Takay H. Toriumi K. Ito T. Souchi Y. Noyori R. J. Am. Chem. Soc. 1980, 102: 7932