8462
L. D’Accolti et al. / Tetrahedron Letters 46 (2005) 8459–8462
Fiorentino, M.; Fusco, C.; Curci, R. J. Am. Chem. Soc.
1989, 111, 6749–6757.
(25 cm · 0.46 cm id) hexane/i-PrOH 98/2, flow 1.5 mL/
min] an ee of 75% was determined.
3. For comprehensive reviews on dioxiranes, see: (a) Curci,
R.; Dinoi, A.; Rubino, M. F. Pure Appl. Chem. 1995, 67,
811–822; (b) Adam, W.; Hadjiarapoglou, L. P.; Curci, R.;
Mello, R. In Organic Peroxides; Ando, W., Ed.; Wiley:
New York, 1992; Chapter 4, pp 195–219.
4. For instance, see: (a) Harrison, D. M. Nat. Prod. Rep.
1988, 5, 387–415; (b) Spencer, T. A. Acc. Chem. Res. 1994,
27, 83–90.
5. (a) Mark, M.; Muller, P.; Maier, R.; Eisele, B. J. Lipid
Res. 1996, 37, 148–158; (b) Morand, O. H.; Aebi, J. D.;
Dehmlow, H.; Ji, J. H.; Gains, N.; Lengsfeld, H.; Himber,
J. J. Lipid Res. 1997, 38, 373–390; (c) Nelson, J. A.;
Steckbeck, S. R.; Spencer, T. A. J. Biol. Chem. 1981, 256,
1067–1068.
11. (a) (R)-2,3-Dihydroxy-2,3-dihydrosqualene (6a): colorless
25
25
oil; ½aꢁD +10.2 (c 1.97, CHCl3) (lit.:11c ½aꢁD +10.7, c 1.6,
CHCl3); 1H NMR (500 MHz, CDCl3) d: 5.13 (m, 5H),
3.35 (dd, 1H, J = 10.2, 2.2 Hz), 2.03 (m, 20H), 1.67 (s,
3H), 1.62 (s, 3H), 1.60 (s, 12H), 1.19 (s, 3H), 1.16 (s, 3H);
{1H}13C NMR (125 MHz, CDCl3) d: 135.1, 134.9, 134.8,
131.2, 125.1, 124.4, 124.2, 78.3, 73.0, 39.7, 39.6, 36.8, 29.6,
28.2, 26.7, 26.6, 26.4, 25.6, 23.2, 17.6, 16.0, 15.9; HRMS
(EI, 70 eV): calcd for C30H52O2: 444.3967, found:
444.3961; IR (neat): 3402, 2922, 1667, 1447, 1383, 1158,
1079, 847 cmꢀ1. Using chiral column HPLC [Chiralcel OD
(25 cm · 0.46 cm id) hexane/i-PrOH 99/1, flow 1.5 mL/
min] an ee of 95% was determined; (b) (S)-2,3-Dihydroxy-
25
2,3-dihydrosqualene (6b): colorless oil; ½aꢁD ꢀ9.5 (c
25
1
6. Xiong, Z.; Corey, E. J. J. Am. Chem. Soc. 2000, 122, 4831–
4832.
1.4, CHCl3) (lit.:11c ½aꢁD ꢀ10.7, c 1.6, CHCl3); H NMR
(500 MHz, CDCl3) d: 5.13 (m, 5H), 3.35 (dd, J = 10.2 Hz,
2.2 Hz), 2.03 (m, 20H) 1.67 (s, 3H), 1.62 (s, 3H), 1.60 (s,
12H), 1.19 (s, 3H), 1.16 (s, 3H); {1H}13C NMR (125 MHz,
CDCl3) d: 135.1, 134.9, 134.8, 131.2 125.1, 124.4, 124.2,
78.3, 73.0, 39.7, 39.6, 36.8, 29.6, 28.2, 26.7, 26.6, 26.4, 25.6,
23.2, 17.6, 16.0, 15.9; HRMS (EI, 70 eV): calcd for
C30H52O2: 444.3967, Found: 444.3959; IR (neat): 3402,
2922, 1667, 1447, 1383, 1158, 1079, 847 cmꢀ1. An ee 89%
was determined by chiral column HPLC [Chiralcel OD
(25 cm · 0.46 cm id) hexane/i-PrOH 99/1, flow 1.5 mL/
min]; (c) Boar, R. B.; Damps, K. J. Chem. Soc., Perkin
Trans. 1 1977, 709–712.
7. (a) Corey, E. J.; Shieh, W.-C. Tetrahedron Lett. 1992, 33,
6435–6438; (b) Corey, E. J.; Noe, M. C.; Shieh, W.-C.
Tetrahedron Lett. 1993, 34, 5995–5998; (c) Huang, A. X.;
Xiong, Z.; Corey, E. J. J. Am. Chem. Soc. 1999, 121, 9999–
10003.
8. (a) Abad, J.; Casas, J.; Sanchez-Baeza, F.; Messeguer, A.
J. Org. Chem. 1993, 58, 3991–3997; (b) Ceruti, M.; Viola,
F.; Dosi, F.; Cattel, L. J. Chem. Soc., Perkin Trans. 1
1988, 461–469; (c) Solvent acetone; column chromatogra-
phy (silica gel, petroleum ether/Et2O 95:5) affords pure
(98%+, HPLC) monooxide 2 (colorless oil, bp164–
165 ꢁC/10 mmHg); spectral data in agreement with
literature.8a
12. Crispino, G. A.; Sharpless, K. B. Tetrahedron Lett. 1992,
33, 4273–4274.
9. Colorless oil (bp183–185 ꢁC/10 mmHg); isolated by
column chromatography (silica gel, petroleum ether/
Et2O 3:1). Spectral data in agreement with literature.8a
10. (a) Squalene 2,3(S)-oxide (2a): colorless oil; bp164–
13. 2,3(S);22(S),23-Dioxide (3a): bp183–185 ꢁC/10 mmHg
(lit.14 83 ꢁC/0.03 mmHg); 1H NMR (CDCl3, 500 MHz)
d: 5.14 (m, 4H), 2.70 (t, 2H, J1 = 6.5 Hz), 2.12–1.97 (m,
16H), 1.69–1.57 (m, 4H), 1.61 (s, 6H), 1.60 (s, 6H) 1.30 (s,
6H), 1.26 (s, 6H); {1H}13C NMR (CDCl3, 125 MHz) d:
134.9, 133.9, 124.9, 124.3, 64.2 (HCO), 58.3 (CO), 39.7,
36.3, 28.2, 27.4, 26.6, 24.9, 18.7, 16.0. IR (neat): 2960,
25
23
165 ꢁC/10 mmHg; ½aꢁD ꢀ1.3 (c 4.89, MeOH) (lit.:7b ½aꢁD
ꢀ1.3, c 0.85, MeOH). Using chiral column HPLC [Chir-
alpak AS (25 cm · 0.46 cm id) hexane/i-PrOH 99/1, flow
0.8 mL/min] an ee of 92% was determined. Spectral data
in agreement with literature7b; (b) Squalene 2,3(R)-oxide
2929, 2848, 1450, 1378, 1260, 1121, 1082, 1026, 800 cmꢀ1
;
HRMS (LDI,TOF): calcd for (C30H50O2+K+): 481.3448,
found: 481.0662 (M+K+); [a]D ꢀ2.2 (c 1.8 CHCl3);
de > 98%, as determined by chiral column HPLC (Chiral-
cel OD, 25 cm · 0.46 cm id, eluent hexane/i-PrOH 98/2,
flow 1.5 mL/min).
25
(2b): colorless oil; bp164–165 ꢁC/10 mmHg; ½aꢁD +1.0
(c 2.1, MeOH); 1H NMR (CDCl3, 500 MHz) d: 512
(m, 5H), 2.70 (t, J = 6.5 Hz, 1H), 2.10–1.97 (m, 20H), 1.68
(s, 3H), 1.61 (s, 3H), 1.59 (s, 12H), 1.29 (s, 3H), 1.25 (s,
3H); {1H}13C NMR (CDCl3, 125 MHz) d 135.1, 134.9,
133.9, 131.2, 124.9, 124.3, 124.2, 64.2, 58.3, 39.7, 39.6,
36.3, 28.2, 27.4, 26.7, 26.6, 25.7, 24.9, 18.7, 17.7, 16.0;
HRMS (LDI,TOF): calcd for (C30H50O+Na+): 449.3759,
found: 449.3748; IR (neat): 2962, 2918, 2855, 1449,
1378 cmꢀ1. Using chiral column HPLC [Chiralcel OD
14. Ichinose, I.; Hosogai, T.; Kato, T. Synthesis 1978, 605–
607.
15. van Tamelen, E. E. Acc. Chem. Res. 1968, 1, 111.
16. Pogliani, L.; Ceruti, M.; Ricchiardi, G.; Viterbo, D. Chem.
Phys Lipids 1994, 70, 21–34, See also references cited
therein.