N. Duguet et al. / Tetrahedron: Asymmetry 21 (2010) 582–600
599
2003, 1948–1949; Maughan, M. A. T.; Davies, I. G.; Claridge, T. D. W.; Courtney,
S.; Hay, P.; Davis, B. G. Angew. Chem., Int. Ed. 2003, 42, 3788–3792.
4.6.4. Table 3 entry 3: (3R,4S)-3-ethyl-4-(naphthalen-2-yl)-3-
phenyl-1-tosylazetidin-2-one (3R,4S)-64 and anti-3-ethyl-4-
(naphthalen-2-yl)-3-phenyl-1-tosylazetidin-2-one anti-65
The b-lactams (3R,4S)-64 and anti-65 were obtained using eth-
ylphenylketene (0.076 g, 0.521 mmol) and 4-methyl-N-(naphtha-
lene-1-ylmethylene)benzenesulfonamide (0.124 g, 0.401 mmol)
following the above general procedure. The reaction mixture was
concentrated after stirring for 16 h at room temperature and the
crude product was purified by silica chromatography, (Et2O/petrol
10:90 then Et2O/petrol 30:70) to give (3R,4S)-64 and anti-65 as col-
ourless solids in a combined yield of 0.161 g (88%). Compound
5. For reviews of stereochemical relay and it applications see: Corminboeuf, O.;
Quaranta, L.; Renaud, P.; Liu, M.; Jasperse, C. P.; Sibi, M. P. Chem. Eur. J. 2003, 9,
28–35; Walsh, P. J.; Lurain, A. E.; Balsells, J. Chem. Rev. 2003, 103, 3297–3344;
Clayden, J.; Vassiliou, N. Org. Biomol. Chem. 2006, 4, 2667–2678; Mikami, K.;
Yamanaka, M. Chem. Rev. 2003, 103, 3369–3400.
6. For representative examples see: Clayden, J.; Pink, J. H.; Yasin, S. A. Tetrahedron
Lett. 1998, 39, 105–108; Betson, M. S.; Clayden, J.; Helliwell, M.; Johnson, P.; Lai,
L. W.; Pink, J. H.; Stimson, C. C.; Vassiliou, N.; Westlund, N.; Yasin, S. A.; Youssef,
L. H. Org. Biomol. Chem. 2006, 4, 424–443; Clayden, J.; Foricher, Y. J. Y.;
Helliwell, M.; Johnson, P.; Mitjans, D.; Vinader, V. Org. Biomol. Chem. 2006, 4,
444–454; Clayden, J.; Westlund, N.; Frampton, C. S.; Helliwell, M. Org. Biomol.
Chem. 2006, 4, 455–461.
7. Hoover, T. R.; Groeper, J. A.; Parrott, R. W., II; Chandrashekar, S. P.; Finefield, J.
M.; Dominguez, A.; Hitchcock, S. R. Tetrahedron: Asymmetry 2006, 17, 1831–
1841; Hoover, T. R.; Hitchcock, S. R. Tetrahedron: Asymmetry 2003, 14, 3233–
3241; Casper, D. M.; Hitchcock, S. R. Tetrahedron: Asymmetry 2003, 14, 517–
521; Casper, D. M.; Burgeson, J. R.; Esken, J. M.; Ferrence, G. M.; Hitchcock, S. R.
Org. Lett. 2002, 4, 3739–3742; Hitchcock, S. R.; Casper, D. M.; Vaughn, J. F.;
Finefield, J. M.; Ferrence, G. M.; Esken, J. M. J. Org. Chem. 2004, 69, 714–718;
Vaughn, J. F.; Hitchcock, S. R. Tetrahedron: Asymmetry 2004, 15, 3449–3455;
Casper, D. M.; Blackburn, J. R.; Maroules, C. D.; Brady, T.; Esken, J. M.; Ferrence,
G. M.; Standard, J. M.; Hitchcock, S. R. J. Org. Chem. 2002, 67, 8871–8876.
8. Sibi, M. P.; Stanley, L. M.; Nie, X.; Venkatraman, L.; Liu, M.; Jasperse, C. P. J. Am.
Chem. Soc. 2007, 129, 395–405; Sibi, M. P.; Venkatraman, L.; Liu, M.; Jasperse, C.
P. J. Am. Chem. Soc. 2001, 123, 8444–8445.
(3R,4S)-64 mp 151–155 °C; ½a D20
¼ ꢀ145:9 (c 1, CH2Cl2, 54% ee);
ꢂ
HPLC analysis: 54% ee (Daicel CHIRALCEL AD-H column, eluent:
hexane/iPrOH 90:10, flow 1 mL minꢀ1, wavelength 254 nm, reten-
tion times: 12.32 min (major S,S) and 41.91 min (minor, R,R)); mmax
(KBr disk)/cmꢀ1: 3063, 2925, 1785 (C@O), 1597, 1512, 1497, 1448,
1368 (S@O), 1172 (S@O), 1010 (S–N), 910 and 738; dH (400 MHz,
CDCl3); 8.00–7.78 (4H, m, ArH), 7.63–7.48 (3H, m, ArH), 7.40–
7.34 (2H, m, ArH), 7.06–7.00 (2H, m, ArH), 6.90–6.70 (5H, m,
ArH), 5.93 (1H, s, TsNCH), 2.48 (3H, s, ArCH3), 2.41–2.23 (2H, m,
CH2) and 0.91 (3H, t, J 7.4, CH2CH3); dC (75 MHz, CDCl3); 168.9,
145.6, 137.5, 134.5, 133.3, 131.2, 130.0, 129.3, 128.4, 127.9,
127.8, 127.3, 126.8, 126.7, 125.7, 125.2, 124.8, 121.8, 71.1, 64.5,
30.5, 21.8 and 9.3; m/z MS (ESI+) 473 ([M+NH4]+, 100); HRMS
(ESI+) C28H29O3N2S1 requires 473.1893, found 473.1889
(ꢀ0.9 ppm). Compound anti-65 mp 130–132 °C; HPLC analysis:
0% ee (Daicel CHIRALCEL AD-H column, eluent: hexane/iPrOH
90:10, flow 1 mL minꢀ1, wavelength 254 nm, retention times:
12.63 min and 14.71 min; mmax (KBr disk)/cmꢀ1: 3040, 2903,
1786 (C@O), 1368 (S@O), 1171 (S@O), 668 and 546; dH
(400 MHz, CDCl3); 7.97 (2H, d, J 8.3, ArH), 7.89 (2H, dd, J 21.4,
8.2, ArH), 7.68 (1H, d, J 7.2, ArH), 7.54–7.47 (3H, m, ArH), 7.48–
7.36 (3H, m, ArH), 7.35–7.26 (3H, m, ArH), 6.99–6.93 (2H, m,
ArH), 5.66 (1H, s, TsNCH), 2.53 (3H, s, ArCH3), 1.66 (1H, dq, J 14.6,
7.3, CHAHB), 1.33 (1H, dq, J 14.6, 7.4, CHAHB) and 0.69 (3H, t, J
7.4, CH2CH3); dC (75 MHz, CDCl3); 168.8, 145.5, 137.9, 135.7,
133.5, 133.1, 131.7, 130.0, 129.1, 128.5, 128.2, 128.0, 127.9,
127.8, 126.8, 126.7, 126.4, 124.7, 69.6, 67.6, 26.9, 21.8 and 8.7;
m/z MS (ESI+) 473 ([M+NH4]+, 100); HRMS (ESI+) C28H29O3N2S1 re-
quires 473.1893, found 473.1890 (ꢀ0.7 ppm).
9. For recent reviews of the ability of NHCs to catalyse organocatalytic processes
see: Enders, D.; Niemeier, O.; Henseler, A. Chem. Rev. 2007, 107, 5606–5655;
Marion, N.; Díez-González, S.; Nolan, S. P. Angew. Chem., Int. Ed. 2007, 46, 2988–
3000.
10. For select examples see: Teles, J. H.; Melder, J.-P.; Ebel, K.; Schneider, R.;
Gehrer, E.; Harder, W.; Brode, S.; Enders, D.; Breuer, K.; Raabe, G. Helv. Chim.
Acta 1996, 79, 61–83; Kerr, M. S.; Read de Alaniz, J.; Rovis, T. J. Am. Chem. Soc.
2002, 124, 10298–10299; Enders, D.; Kallfass, U. Angew. Chem., Int. Ed. 2002, 41,
1743–1745; Hachisu, Y.; Bode, J. W.; Suzuki, K. Adv. Synth. Catal. 2004, 346,
1097–1100; Mattson, A. E.; Bharadwaj, A. R.; Zuhl, A. M.; Scheidt, K. A. J. Org.
Chem. 2006, 71, 5715–5724; Myers, M. C.; Bharadwaj, A. R.; Milgram, B. C.;
Scheidt, K. A. J. Am. Chem. Soc. 2005, 127, 14675–14680; Moore, J. L.; Kerr, M. S.;
Rovis, T. Tetrahedron 2006, 62, 11477–11482; Mattson, A. E.; Scheidt, K. A. J.
Am. Chem. Soc. 2007, 129, 4508–4509; Orellana, A.; Rovis, T. Chem. Commun.
2008, 730–732; Read de Alaniz, J.; Kerr, M. S.; Moore, J. L.; Rovis, T. J. Org. Chem.
2008, 73, 2033–2040; Wong, F. T.; Patra, P. K.; Seayad, J.; Zhang, Y.; Ying, J. Y.
Org. Lett. 2008, 10, 2333–2336; Cullen, S. C.; Rovis, T. Org. Lett. 2008, 10, 3141–
3144; Liu, Q.; Perreault, S.; Rovis, T. J. Am. Chem. Soc. 2008, 130, 14066–14067.
11. For select examples see: Chow, K. Y.-K.; Bode, J. W. J. Am. Chem. Soc. 2004, 126,
8126–8127; Reynolds, N. T.; Read de Alaniz, J.; Rovis, T. J. Am. Chem. Soc. 2004,
126, 9518–9519; Chan, A.; Scheidt, K. A. Org. Lett. 2005, 7, 905–908; Zeitler, K.
Angew. Chem., Int. Ed. 2005, 44, 7506–7510; Reynolds, N. T.; Rovis, T. J. Am.
Chem. Soc. 2005, 127, 16406–16407; Sohn, S. S.; Bode, J. W. Org. Lett. 2005, 7,
3873–3876; Sohn, S. S.; Bode, J. W. Angew. Chem., Int. Ed. 2006, 45, 6021–6024;
Vora, H. U.; Rovis, T. J. Am. Chem. Soc. 2007, 129, 13767–13796; Bode, J. W.;
Sohn, S. S. J. Am. Chem. Soc. 2007, 129, 13798–13799; Vora, H. U.; Moncecchi, J.
R.; Epstein, O.; Rovis, T. J. Org. Chem. 2008, 73, 9727–9731; Noonan, C.;
Baragwanath, L.; Connon, S. J. Tetrahedron Lett. 2008, 49, 4003–4006.
12. Maki, B. E.; Chan, A.; Phillips, E. M.; Scheidt, K. A. Org. Lett. 2007, 9, 371–374;
Maki, B. E.; Scheidt, K. A. Org. Lett. 2008, 10, 4331–4334; Maki, B. E.; Chan, A.;
Phillips, E. M.; Scheidt, K. A. Tetrahedron 2009, 65, 3102–3109.
Acknowledgements
The authors would like to thank the Royal Society for a Univer-
sity Research Fellowship (A.D.S.), AstraZeneca and the EPSRC (Case
studentship to J.D.), GlaxoSmithKline (Case studentship to A.D.),
Pfizer (Case studentship to S.M.L.) and The Leverhulme Trust
(N.D.) for funding. The EPSRC mass spectrometry facility is also
acknowledged.
13. For examples see: Burstein, C.; Glorius, F. Angew. Chem., Int. Ed. 2004, 43, 6205–
6208; Sohn, S. S.; Rosen, E. L.; Bode, J. W. J. Am. Chem. Soc. 2004, 126, 14370–
14371; Chan, A.; Scheidt, K. A. Org. Lett. 2005, 7, 905–908; He, M.; Bode, J. W.
Org. Lett. 2005, 7, 3131–3134; Chan, A.; Scheidt, K. A. J. Am. Chem. Soc. 2007,
129, 5334–5335; Phillips, E. M.; Reynolds, T. E.; Scheidt, K. A. J. Am. Chem. Soc.
2008, 130, 2416–2417; Chan, A.; Scheidt, K. A. J. Am. Chem. Soc. 2008, 130,
2740–2741; Rommel, M.; Fukuzumi, T.; Bode, J. W. J. Am. Chem. Soc. 2008, 130,
17266–17267; Liu, Q.; Rovis, T. Org. Lett. 2009, 11, 2856–2859; For the use of
a’-hydroxyenones as a,b-unsaturated aldehyde surrogates see: Chiang, P.-C.;
Rommel, M.; Bode, J. W. J. Am. Chem. Soc. 2009, 131, 8714–8718.
14. He, M.; Struble, J. R.; Bode, J. W. J. Am. Chem. Soc. 2006, 128, 8418–8420; He, M.;
Uc, G. J.; Bode, J. W. J. Am. Chem. Soc. 2006, 128, 15088–15089; Phillips, E. M.;
Wadamoto, M.; Chan, A.; Scheidt, K. A. Angew. Chem., Int. Ed. 2007, 46, 3107–
3110; He, M.; Beahm, B. J.; Bode, J. W. Org. Lett. 2008, 10, 3817–3820.
15. For select examples see: Song, J. J.; Gallou, F.; Reeves, J. T.; Tan, Z.; Yee, N. K.;
Senanayake, C. H. J. Org. Chem. 2006, 71, 1273–1276; Suzuki, Y.; Abu Bakar, M.
D.; Muramatsu, K.; Sato, M. Tetrahedron 2006, 62, 4227–4231; Kano, T.; Sasaki,
K.; Konishi, T.; Mii, H.; Maruoka, K. Tetrahedron Lett. 2006, 47, 4615–4618.
16. Alcaide, B.; Almendros, P.; Cabrero, G.; Ruiz, M. P. Chem. Commun. 2007, 4788–
4790; Li, G.-Q.; Li, Y.; Dai, L.-X.; You, S.-L. Org. Lett. 2007, 9, 3519–3521; Li, G.-
Q.; Li, Y.; Dai, L.-X.; You, S.-L. Adv. Synth. Catal. 2008, 350, 1258–1262; Wang, L.;
Thai, K.; Gravel, M. Org. Lett. 2009, 11, 891–893; Li, G.-Q.; Dai, L.-X.; You, S.-L.
Org. Lett. 2009, 11, 1623–1625; Domingo, L. R.; Aurell, M. J.; Arno, M.
Tetrahedron 2009, 65, 3432–3440.
References
1. Bull, S. D.; Davies, S. G.; Epstein, S. W.; Ouzman, J. V. A. Chem. Commun. 1998,
659–660; Bull, S. D.; Davies, S. G.; Epstein, S. W.; Leech, M. A.; Ouzman, J. V. A. J.
Chem. Soc., Perkin Trans. 1 1998, 2321–2330.
2. Bull, S. D.; Davies, S. G.; Fox, D. J.; Sellers, T. G. R. Tetrahedron: Asymmetry 1998,
9, 1483–1487.
3. Bull, S. D.; Davies, S. G.; Fox, D. J.; Garner, A. C.; Sellers, T. G. R. Pure Appl. Chem.
1998, 70, 1501–1506.
4. For select examples of ‘chiral relay’ in asymmetric transformations see:
Watanabe, Y.; Mase, N.; Furue, R.; Toru, T. Tetrahedron Lett. 2001, 42, 2981–
2984; Davis, T. J.; Balsells, J.; Carroll, P. J.; Walsh, P. J. Org. Lett. 2001, 3, 2161–
2164; Balsells, J.; Walsh, P. J. J. Am. Chem. Soc. 2000, 122, 1802–1803; Evans, D.
A.; Campos, K. R.; Tedrow, J. S.; Michael, FE.; Gagne, M. R. J. Am. Chem. Soc. 2000,
122, 7905–7920; Hiroi, K.; Ishii, M. Tetrahedron Lett. 2000, 41, 7071–7074;
Wada, E.; Pei, W.; Kanemasa, S. Chem. Lett. 1994, 2345–2348; Wada, E.;
Yasuoka, H.; Kanemasa, S. Chem. Lett. 1994, 1637–1640; Malkov, A. V.; Stoncius,
S.; MacDougall, K. N.; Mariani, A.; McGeoch, G. D.; Kocovsky, P. Tetrahedron
2006, 62, 264–284; Malkov, A. V.; Hand, J. B.; Kocovsky, P. Chem. Commun.
17. For transesterification see: Grasa, G. A.; Kissling, R. M.; Nolan, S. P. Org. Lett.
2002, 4, 3583–3586; Grasa, G. A.; Güveli, T.; Singh, R.; Nolan, S. P. J. Org. Chem.
2003, 68, 2812–2819; Connor, E. F.; Nyce, G. W.; Myers, M.; Möck, A.; Hedrick,
J. L. J. Am. Chem. Soc. 2002, 124, 914–915; Nyce, G. W.; Lamboy, J. A.; Connor, E.