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LETTER
(7) (a) Katoh, T.; Kirihara, M.; Nagata, Y.; Kobayashi, Y.; Arai,
K.; Minami, J.; Terashima, S. Tetrahedron 1994, 50, 6239.
(b) Katoh, T.; Kirihara, M.; Nagata, Y.; Kobayashi, Y.; Arai,
K.; Minami, J.; Terashima, S. Tetrahedron Lett. 1993, 34,
5747.
a solution of DMS (–78 °C, 186 mg, 3 mmol) in CH2Cl2 (1
mL) was added dropwise and the reaction mixture was
warmed to r.t. The mixture was then washed with brine
(3 × 30 mL) and the aqueous layers were extracted with 30
mL of CH2Cl2. The organic layers were combined and dried
over Na2SO4. After removal of the solvents, the residue was
chromatographed over silica gel (eluent: cyclohexane–
EtOAc, 95:5 to 75:25) to afford epoxide 9 (de 82%; major
isomer: 89 mg, 0.21 mmol; minor isomer: 9 mg, 0.02 mmol)
as a colourless oil. Major diastereomer : [a]D20 –48.1 (c 1.0,
C6H6). 1H NMR (CDCl3): d = 2.24–2.40 (dd, J = 5.3, 13.6
Hz 1 H, CH2Bn), 2.74 (dd, J = 2.9, 5.9 Hz, 1 H, CH2-O-CH),
2.95–3.15 (m, 1 H, NTroc-CH2-CH-C=Oketone), 3.24 (dd,
J = 4.2, 5.9 Hz, 1 H, CH2-O-CH), 3.35 (dd, J = 3.5, 13.6 Hz,
(8) Schneider, U.; Pannecoucke, X.; Quirion, J.-C. Synlett 2002,
1669.
(9) (a) Li, G.; Lenington, R.; Willis, S.; Kim, S. H. J. Chem.
Soc., Perkin Trans. 1 1998, 1753. (b) Reddy, K. L.;
Sharpless, K. B. J. Am. Chem. Soc. 1998, 120, 1207. (c) Li,
G.; Angert, H. H.; Sharpless, K. B. Angew. Chem., Int. Ed.
Engl. 1996, 35, 2813.
(10) (a) O’Brien, P.; Osborne, S. A.; Parker, D. D. Tetrahedron
Lett. 1998, 39, 4099. (b) O’Brien, P.; Osborne, S. A.;
Parker, D. D. J. Chem. Soc., Perkin Trans. 1 1998, 2519.
(11) (a) Harnisch, J.; Szeimies, G. Chem. Ber. 1979, 112, 3914.
(b) Cavender, C. J.; Shiner, V. J. Jr. J. Org. Chem. 1972, 37,
3567.
(12) (a) Kolb, H. C.; VanNieuwenhze, M. S.; Sharpless, K. B.
Chem. Rev. 1994, 94, 2483. (b) Crispino, G. A.; Jeong, K.-
S.; Kolb, H. C.; Wang, Z.-M.; Xu, D.; Sharpless, K. B. J.
Org. Chem. 1993, 58, 3785. (c) Sharpless, K. B.; Amberg,
W.; Bennami, Y. L.; Crispino, G. A.; Hartung, J.; Jeong, K.-
S.; Kwong, H.-L.; Morikawa, K.; Wang, Z.-M.; Xu, D.;
Zhang, X.-L. J. Org. Chem. 1992, 57, 2768.
1 H, CH2Bn), 3.62–3.79 (m, 4 H, NTroc-CH2-CH-C=Oketone
NTroc-CH2-C=Oketone), 3.72 (s, 3 H, O-CH3), 3.86 (dd,
J = 2.9, 4.2 Hz, 1 H, CH2-O-CH), 4.79 (s, 2 H, CH2Troc),
,
7.19–7.60 (m, 3 H, 3 × CHAr). 13C NMR (CDCl3): d = 32.2
(CH2Bn), 48.1 (NTroc-CH2-CH-C=Oketone), 50.5 (NTroc-CH2-
CH-C=Oketone), 51.2 (CH2-O-CH), 51.7 (CH2-O-CH), 52.1
(NTroc-CH2-C=Oketone), 55.9 (O-CH3), 75.1 (CH2Troc), 95.1
(CCl3Troc), 128.6 (CHAr), 130.1 (CHAr), 130.9 (CHAr), 134.1
(CAr), 135.6 (CAr), 138.0 (CAr), 152.9 (C=OTroc), 210.1
(C=Oketone). IR (film): 3053, 3028, 2854, 1745, 1694, 1609,
1497, 1255, 1132, 909, 804, 790, 686 cm–1.
(13) (a) Johnson, R. A.; Sharpless, K. B. Catalytic Asymmetric
Synthesis; Ojima, I., Ed.; VCH: New York, 1993, Chap. 4.4.
(b) Kolb, H. C.; Sharpless, K. B. Tetrahedron Lett. 1992, 48,
10515. (c) Zhou, B.; Edmondson, S.; Padron, J.;
Danishefsky, S. J. Tetrahedron Lett. 2000, 41, 2039.
(14) (a) Pedragosa-Moreau, S.; Archelas, A.; Furstoss, R. J. Org.
Chem. 1993, 58, 5533. (b) Chen, X.-J.; Archelas, A.;
Furstoss, R. J. Org. Chem. 1993, 58, 5528. (c) Barili, P. L.;
Berti, G.; Mastrorilli, E. Tetrahedron 1993, 49, 6263.
(d) Sinha, S. C.; Keinan, E.; Reymond, J. L. J. Am. Chem.
Soc. 1993, 115, 4893. (e) Jacobsen, E. N. Acc. Chem. Res.
2000, 33, 421.
(15) (a) Jacobsen, E. N. Comprehensive Organometallic
Chemistry II, Vol. 12; Wilkinson, G.; Stone, F. G. A.; Abel,
E. W.; Hegedus, L. S., Eds.; Pergamon: New York, 1995,
Chap. 11.1. (b) Jacobsen, E. N. Catalytic Asymmetric
Synthesis; Ojima, I., Ed.; VCH: New York, 1993, Chap. 4.2.
(16) (a) Palucki, M.; McCormick, G. J.; Jacobsen, E. N.
Tetrahedron Lett. 1995, 36, 5457. (b) Palucki, M.; Pospisil,
P. J.; Zhang, W.; Jacobsen, E. N. J. Am. Chem. Soc. 1994,
116, 9333.
(19) Synthesis of b-Azidoalcohol 4a.
A mixture of enantiopure styrene oxide 9 (211 mg, 0.5
mmol), NaN3 (65 mg, 1.0 mmol) and NH4Cl (67 mg, 1.25
mmol) in EtOH (1 mL)–H2O (0.25 mL) was refluxed during
24 h. The reaction mixture was cooled to r.t., H2O (4 mL)
was added. The aqueous layer was then extracted with
CH2Cl2 (3 × 5 mL). The combined organic layers were dried
over Na2SO4 and concentrated under reduced pressure. The
residue was chromatographed over silica gel (eluent:
cyclohexane–EtOAc, 90:10 to 50:50) to afford b-
azidoalcohol 4a (de 85%; major isomer: 118.5mg, 0.26
mmol; minor isomer: 9.5 mg, 0.02 mmol) as a pale yellow
oil. Major diastereomer: [a]D20 +47.9 (c 1.0, C6H6). 1H NMR
(CDCl3): d = 2.15 (s, 1 H, CH2-OH), 2.21–2.40 (dd, J = 5.2,
13.7 Hz, 1 H, CH2Bn), 2.90–3.06 (m, 1 H, NTroc-CH2-CH-
C=Oketone), 3.26 (dd, J = 3.5, 13.7 Hz, 1 H, CH2Bn), 3.70–
4.12 (m, 6 H, NTroc-CH2-CH-C=Oketone, NTroc-CH2-C=Oketone
,
CH2-OH), 3.80 (s, 3 H, O-CH3), 4.81 (s, 2 H, CH2Troc), 4.95
(t, J = 6.3 Hz, 1 H, CH-N3), 7.20–7.51 (m, 3 H, 3 × CHAr).
13C NMR (CDCl3): d = 32.2 (CH2Bn), 47.9 (NTroc-CH2-CH-
C=Oketone), 50.5 (NTroc-CH2-CH-C=Oketone), 52.2 (NTroc-CH2-
C=Oketone), 56.0 (O-CH3), 63.8 (CH-N3), 66.3 (CH2-OH),
75.0 (CH2Troc), 95.2 (CCl3Troc), 128.6 (CHAr), 129.8 (CHAr),
130.9 (CHAr), 134.1 (CAr), 135.6 (CAr), 137.7 (CAr), 153.0
(C=OTroc), 209.8 (C=Oketone). IR (film): 3396, 3030, 2946,
2859, 2097, 1737, 1693, 1606, 1499, 1354, 1082, 803, 690
cm–1. Anal. Calcd for C17H19Cl3N4O5: C, 43.84; H, 4.11; N,
12.03. Found: C, 44.10; H, 3.93; N, 11.85.
(17) Brandes, B. D.; Jacobsen, E. N. Tetrahedron: Asymmetry
1997, 8, 3927.
(18) Synthesis of Epoxide 9.
MCPBA (104 mg, 0.6 mmol) was added by portion over a
period of 2 min to a –78 °C stirred solution of styrene 5b (86
mg, 0.3 mmol), NMO (176 mg, 1.5 mmol) and Jacobsen’s
catalyst (R,R)-8 (20 mg, 0.03 mmol) in CH2Cl2 (1 mL). The
reaction was vigourously stirred during 2 h at –78 °C. Then
Synlett 2005, No. 12, 1853–1856 © Thieme Stuttgart · New York