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T. J. Donohoe et al. / Tetrahedron Letters 50 (2009) 3523–3526
2. (a) Piccialli, V. Synthesis 2008, 2585; (b) Donohoe, T. J.; Churchill, G. H.;
Wheelhouse (neé Gosby), K. M. P.; Glossop, P. A. Angew. Chem., Int. Ed. 2006, 45,
8025; (c) Donohoe, T. J.; Butterworth, S. Angew. Chem., Int. Ed. 2005, 44, 4766;
(d) Donohoe, T. J.; Butterworth, S. Angew. Chem., Int. Ed. 2003, 42, 948.
3. (a) Chang, H.-T.; Li, G.; Sharpless, K. B. Angew. Chem., Int. Ed. 1996, 35, 2813; (b)
Rubins, A. E.; Sharpless, K. B. Angew. Chem., Int. Ed. 1997, 36, 2637; For a review
on the asymmetric aminohydroxylation reaction see: (c) Bodkin, J. A.; McLeod,
M. D. J. Chem. Soc., Perkin Trans. 1 2002, 2733.
4. (a) Donohoe, T. J.; Bataille, C. J. R.; Gattrell, W.; Kloesges, J.; Rossignol, E. Org.
Lett. 2007, 9, 1725; (b) Donohoe, T. J.; Chughtai, M. J.; Klauber, D. J.; Griffin, D.;
Campbell, A. D. J. Am. Chem. Soc. 2006, 128, 2514.
5. Donohoe, T. J.; Wheelhouse (neé Gosby), K. M. P.; Lindsay-Scott, P. J.; Glossop, P.
A.; Nash, I. A.; Parker, J. S. Angew. Chem., Int. Ed. 2008, 47, 2872.
(CDCl3, 400 MHz) d 5.92 (1H, s), 4.81 (1H, ddd, J 8.6, 6.3, 4.6 Hz), 4.38 (1H, t, J
8.7 Hz), 4.02 (1H, dd, J 9.0, 5.2 Hz), 3.99–3.94 (1H, m), 3.92–3.87 (1H, m), 3.72
(1H, td, J 8.5, 5.2 Hz), 2.09 (3H, s), 2.04–1.96 (2H, m), 1.65–1.47 (4H, m), 1.33–
1.21 (6H, m), 0.86 (3H, t, J 6.8 Hz); 13C NMR (CDCl3, 100 MHz) d 171.3, 159.1,
81.0, 80.8, 75.9, 66.3, 56.1, 31.6, 30.9, 27.6, 27.6, 24.9, 22.5, 21.3, 14.0; mmax
(thin film)/cmÀ1 3287, 2955, 2931, 2861, 1758, 1466, 1408, 1374, 1243, 1126,
1058, 1026, 946, 922; m/z (ESI+) 358 (100%, [M+NH4+MeCN])+; HMRS (ESI+)
C15H25O5NNa requires [M+Na]+ 322.1630, found 322.1641 (2.5 ppm).
Data for compound 16: hydroxamic ester 13 (135 mg, 0.391 mmol) was
subjected to general procedure 1. Purification by flash column
chromatography (SiO2, eluting with 7:3 petrol/ethyl acetate, Rf 0.30 in ethyl
acetate) gave tetrahydrofuran 16 (90 mg, 0.350 mmol, 90%) as an oil. 1H NMR
(CDCl3, 400 MHz) d 6.06 (1H, s), 4.89–4.85 (1H, m), 4.41 (1H, t, J 8.8 Hz), 4.08
(1H, dd, J 8.9, 5.5 Hz), 4.00–3.96 (1H, m), 3.92–3.86 (1H, m), 3.76–3.70 (1H, m),
2.06 (3H, s), 2.01–1.93 (2H, m), 1.84–1.75 (1H, m), 1.67–1.50 (3H, m), 0.89 (3H,
t, J 7.5 Hz); 13C NMR (CDCl3, 100 MHz) d 170.7, 159.4, 80.8, 80.4, 75.5, 66.4,
56.2, 26.9, 26.6, 24.0, 21.1, 9.7; mmax (thin film)/cmÀ1 3286, 2970, 1749, 1411,
1373, 1240, 1080, 1023, 963, 925; m/z (ESI+) 258 (60%, [M+H])+, 532 (90%,
[2M+NH4])+, 537 (100%, [2M+Na])+; HMRS (ESI+) C12H19O5NNa requires
[M+Na]+ 280.1155, found 280.1155 (0.08 ppm).
6. Wai, J. S. M.; Markó, I.; Svendsen, J. M.; Finn, M. G.; Jacobsen, E. N.; Sharpless, K.
B. J. Am. Chem. Soc. 1989, 111, 1123.
7. Wasilke, J.-C.; Obrey, S. J.; Baker, R. T.; Bazan, G. C. Chem. Rev. 2005, 105, 1001.
8. Still, W. C.; Gennari, C. Tetrahedron Lett. 1983, 24, 4405.
9. General procedure 1: One-pot TA/oxidative cyclisation: potassium osmate
dihydrate (0.01 equiv) was added to
a solution of the hydroxamic ester
(1 equiv) in a 3:1 mixture of acetonitrile–water (20 mL per mmol substrate)
and the reaction mixture stirred at 50 °C for 2 h. ( )-Camphor-10-sulfonic acid
(6 equiv), pyridine N-oxide (2 equiv) and citric acid (0.75 equiv) were added and
the reaction mixture stirred at 50 °C for a further 16 h. The reaction was
quenched by addition of solid sodium sulfite (10 mg), stirred for 30 min, washed
with aqueous 2 M sodium hydroxide (5 mL) and extracted with ethyl acetate
(3 Â 5 mL). The combined organic extracts were dried over sodium sulfate,
filtered and concentrated. The residue was dissolved in pyridine (1 mL) and
acetic anhydride (1 mL) and the resultant mixture stirred at room temperature
for 16 h. The reaction mixture was concentrated and the crude product purified
by flash column chromatography. The beneficial effect of citric acid on osmium-
catalysed processes has been documented; see Dupau, P.; Epple, R.; Thomas, A.
A.; Fokin, V. V.; Sharpless, K. B. Adv. Synth. Catal. 2002, 344, 421.
11. Data were collected at low temperature using an Enraf-Nonius KCCD
diffractometer [Otwinowski, Z.; Minor, W. Processing of X-ray Diffraction
Data Collected in Oscillation Mode, In Methods Enzymol. Carter, C. W., Sweet, R.
M., Eds.; Academic Press, 1997, Vol. 276.]. The Crystal structures were solved
using SIR92 [Altomare, A.; Cascarano, G.; Giacovazzo, C.; Guagliardi, A.; Burla,
M.C.; Polidori, G.; Camalli, M. J. Appl. Crystallogr. 1994, 27, 435.] and refined
using the CRYSTALS software suite [Betteridge, P.W.; Carruthers, J.R.; Cooper,
R.I.; Prout, K.; Watkin, D.J. J. Appl. Crystallogr. 2003, 36, 1487.], as per the CIF.
Crystallographic data (excluding structure factors) for this compound have
been deposited with the Cambridge Crystallographic Data Centre (CCDC
721466) and copies of these data can be obtained free of charge via
10. Data for compound 15: hydroxamic ester 11 (111 mg, 0.286 mmol) was
subjected to general procedure 1. Purification by flash column
chromatography (SiO2, eluting with 7:3 petrol/ethyl acetate, Rf 0.38 in ethyl
acetate) gave tetrahydrofuran 15 (75 mg, 0.250 mmol, 87%) as an oil. 1H NMR
12. (a) Piccialli, V.; Caserta, T.; Caruso, L.; Gomez-Paloma, L.; Bifulco, G. Tetrahedron
2006, 62, 10989; (b) Piccialli, V.; Cavallo, N. Tetrahedron Lett. 2001, 42, 4695.
13. Donohoe, T. J.; Harris, R. M.; Burrows, J. N.; Parker, J. S. J. Am. Chem. Soc. 2006,
128, 13704.