1816
T. Berkenbusch, R. Brücknerb
LETTER
(9) Compound 16 has been previously prepared, see ref.7a
(10) Except for compound 24, all new compounds gave
satisfactory 1H NMR and IR spectra as well as correct
combustion analyses.
(11) (a) Rieke, R. D.; Uhm, S. J.; Hudnall, P. M. J. Chem. Soc.,
Chem. Commun. 1973, 269. (b) Rieke, R. D.; Uhm, S. J.
Synthesis 1975, 452.
(12) Procedure: (a) Avignon-Tropis, M.; Pougny, J. R.
Tetrahedron Lett. 1989, 30, 4951. (b) Chou, W.-N.; Clark,
D. L.; White, J. B. Tetrahedron Lett. 1991, 32, 299.
(13) (a) Johnson, R. A.; Sharpless, K. B. In Catalytic Asymmetric
Synthesis; Ojima, I. E., Ed.; Wiley-VCH: New York, 1993,
103–158. (b) Katsuki, T.; Martin, V. S. Org. React. 1996,
48, 1.
(14) SAEs of cis-2-butene-1,4-diol mono-protected with a tert-
butyldimethylsilyl roup: (a) Astles, P. C.; Thomas, E. J. J.
Chem. Soc., Perkin Trans. 1 1997, 845; 85% ee.
(b) Shibuya, H.; Kawashima, K.; Narita, N.; Ikeda, M.;
Kitagawa, I. Chem. Pharm. Bull. 1992, 40, 1154; 84–85%
ee.
(22) cis-(2S,4R)-1,7-Bis-[(4-methoxybenzyl)oxy]-5-heptene-
2,4-diol (ent-21): [a]D25 = 14.8 (c = 0.78 in CHCl3).
1H NMR (500.0 MHz, CDCl3): d = AB signal (dA = 1.55,
dB = 1.71, JAB = 14.2 Hz, in addition split by JA,4 = 4.4 Hz,
JA,2 = 2.7 Hz, JB,2 = 9.9 Hz, JB,4 = 8.8 Hz, 3-H2), 3.07 (br s, 2
× OH), AB signal (dA = 3.35, dB = 3.40, JAB = 9.5 Hz, in
addition split by JA,2 = 7.1 Hz, JB,2 = 4.1 Hz, 1-H2), 3.795 and
3.804 (2 × s, 2 × OCH3), 3.96 (mc, 2-H), AB signal (dA =
4.06, dB = 4.09, JAB = 12.4 Hz, in addition split by JA,6 = 6.1
Hz, 4JA,5-H = 1.3 Hz, JB,6 = 6.4 Hz, JB,5-H = 1.3 Hz, 7-H2), AB
signal (dA = 4.43, dB = 4.46, JAB = 11.2 Hz, 1¢-H2), B part
partly superimposed by 4.47 (s, 1¢¢-H2), 4.67 (ddd with
incompletely resolved allylic couplings, J4,5 = J4,3-H(B) = 8.4
Hz, J4,3-H(A) = 4.2 Hz, 4-H), 5.60 (dddd, Jcis = 11.4 Hz, J5,4
8.0 Hz, 4J5,7-H(A) = 4J5,7-H(B) = 1.3 Hz, 5-H), 5.68 (dddd, Jcis
11.2 Hz, J6,7-H(A) = J6,7-H(B) = 6.2 Hz, 4J6,4 = 0.9 Hz, 6-H),
=
=
AA¢BB¢ signal centered at d = 6.87 and d = 7.25 (2 × C6H4).
13C NMR (125.7 MHz, CDCl3): d = 39.74 (C-3), 55.26 (2 ×
OCH3), 65.54, 67.63, 70.20, 72.19, 73.06 and 74.00 (C-1, C-
2, C-4, C-7, C-1¢, C-1¢¢), 113.85, 127.69, 129.40, 129.50,
129.93, 129.97, 135.72, 159.32, and 159.33 (9 resonances
for 10 non-equivalent nuclei: C-5, C-6, 2 × C6H4).
IR(film): 3400, 3000, 2920, 2855, 1615, 1585, 1515, 1465,
1455, 1445, 1420, 1360, 1300, 1245, 1175, 1075, 1030, 820
cm–1.
(15) SAEs of cis-2-butene-1,4-diol mono-protected with a PMB
group: (a) Williams, R. M.; Rollins, S. B.; Judd, T. C.
Tetrahedron 2000, 56, 521; 88% ee. (b) Yoshino, T.;
Nagata, Y.; Itoh, E.; Hashimoto, M.; Katoh, T.; Terashima,
S. Tetrahedron 1997, 53, 10239; 85% ee.
(16) This was concluded from the integral ratio of the peaks
Anal. Calcd for C23H30O6 (402.5): C, 68.64; H, 7.51. Found:
C, 68.34; H, 7.24.
(23) Regioselective reductions of a,b-epoxy alcohols resulting in
1,3-diols (Red-Al®-method) or 1,2-diols (DIBAL-method):
(a) Finan, J. M.; Kishi, Y. Tetrahedron Lett. 1982, 23, 2719.
(b) Viti, S. M. Tetrahedron Lett. 1982, 23, 4541.
attributed to 3-H [dmajor = 3.02 (dd; 19/ent-19), dminor
3.08(dd)].
=
(17) Still, W. C.; Kahn, M.; Mitra, A. J. Org. Chem. 1978, 43,
2923.
(18) In addition, we retrieved inseparable mixtures of mono- with
bis-epoxides.
(24) (2R,4R)-1-[(4-Methoxybenzyl)oxy]-6-heptene-2,4-diol
(19) This was concluded from the integral ratio of the peaks
(22): [a]D25 = –1.9 (c = 0.81 in CHCl3).
attributed to 3-H [dmajor = 3.00 (dd; 20/ent-20), dminor
3.06(dd)].
=
1H NMR (500.0 MHz, CDCl3): d = AB signal (dA = 1.53,
dB = 1.62, JAB = 14.4 Hz, in addition split by JA,2 = JA,4 = 9.8
Hz, JB,2 = JB,4 = 2.7 Hz, 3-H2), 2.25 (dddd, J5,6 = 7.3 Hz, J5,4
= 6.2 Hz, 4J5,7-H(E) = 4J5,7-H(Z) = 1.1 Hz, 5-H2), 2.91–3.28 (m,
2 × OH), AB signal (dA = 3.35, dB = 3.43, JAB = 9.4 Hz, in
addition split by JA,2 = 7.1 Hz, JB,2 = 3.9 Hz, 1-H2), 3.81 (s,
OCH3), 3.92 (dtd with transition to higher order splitting,
(20) cis-(2R,3S,4S)-2,3-Epoxy-1,7-bis-[4-methoxybenzyl)oxy]-
5-hepten-4-ol(20): [a]D25 = –30.9 (c = 0.58 in CHCl3);
– 94.4% ee by HPLC.
1H NMR (500.0 MHz, CDCl3): d = 2.80 (d, JOH,4 = 2.3 Hz,
OH), 3.00 (dd, J3,4 = 7.5 Hz, J3,2 = 4.3 Hz, 3-H), 3.25 (mc,
probably incompletely resolved ddd: J2,1-H(A) = J2,1-H(B)
=
J
4,3-H(A) = 9.8 Hz, J4,5 = 6.1 Hz, J4,3-H(B) = 2.5 Hz, 4-H), 4.04
(dddd, J2,3-H(A) = 10.4 Hz, J2,1-H(A) = 6.6 Hz, J2,1-H(B) = 3.8 Hz,
J2,3-H(B) = 3.1 Hz, 2-H), 4.48 (s, 1¢-H2), 5.09–5.14 (m, 7-HE,
ca. 5.7 Hz, J2,3 = 4.3 Hz, 2-H), AB signal (dA = 3.63, dB =
3.79, JAB = 11.1 Hz, in addition split by JA,2 = 6.2 Hz, JB,2
=
5.4 Hz, 1-H2), B part superimposed by 3.80 (s, 2 × OCH3),
7-HZ), 5.82 (mc, 6-H), AA¢BB¢ signal centered at d = 6.88
and d = 7.25 (C6H4).
AB signal (dA = 4.05, dB = 4.11, JAB = 12.9 Hz, in addition
split by JA,6 = 5.7 Hz, 4JA,5-H = 1.4 Hz, JB,6 = 6.7 Hz, 4JB,5-H
1.5 Hz, 7-H2), 4.25 (br dd, J4,3 = J4,5 = 7.5 Hz, 4-H), 4.42
(s, 1¢¢-H2)*, AB signal (dA = 4.46, dB = 4.54, JAB = 11.4 Hz,
=
13C NMR (125.7 MHz, CDCl3): d = 38.71 and 42.21 (C-3, C-
5), 55.26 (OCH3), 71.02, 71.16, 73.05, and 73.99 (C-1, C-2,
C-4, C-1¢), 113.86 and 129.41 (2 × Cortho, 2 × Cmeta), 117.86,
129.89, 134.51, and 159.35 (C-6, C-7, Cpara, Cipso).
IR(film): 3400, 3075, 2915, 2860, 1640, 1615, 1585, 1515,
1460, 1440, 1365, 1300, 1250, 1175, 1100, 1035, 990, 920,
820 cm–1.
1¢-H2), 5.70 (dddd, Jcis = 11.3 Hz, J5,4 = 7.6 Hz, 4J5,7-H(A)
=
4J5,7-H(B) = 1.5 Hz, 5-H), 5.82 (br ddd, Jcis = 11.4 Hz,
J6,7-H(A) = J6,7-H(B) = 6.0 Hz, 6-H), AA¢BB¢ signal centered at
d = 6.88 and d = 7.26 (2 × C6H4).
13C NMR (125.8 MHz, CDCl3): d = 54.73 (C-2), 55.26 (2 ×
OCH3), 58.12 (C-3), 65.80 (C-7), 66.34 (C-4), 68.00 (C-1),
72.02 (C-1¢¢), 73.20 (C-1¢), 113.83, 113.96, 129.46, and
129.60 (2 × 2 × Cortho, 2 × 2 × Cmeta), 129.32, 130.03, 159.28,
and 159.51 (2 × Cpara, 2 × Cipso), 130.29 (C-6), 131.71 (C-5).
IR(film): 3400, 3000, 2935, 2910, 2860, 2835, 1610, 1585,
1515, 1460, 1300, 1250, 1175, 1075, 1035, 850, 820 cm–1.
Anal. Calcd for C23H28O6 (400.5): C, 68.98; H, 7.05. Found
C, 68.99; H, 7.20.
Anal. Calcd for C15H22O4 (266.3): C, 67.64; H, 8.33. Found:
C, 67.54; H, 8.39.
(25) (a) Rychnovsky, S. D.; Skalitzky, D. J. Tetrahedron Lett.
1990, 31, 945. (b) Rychnovsky, S. D.; Rogers, B.; Yang, G.
J. Org. Chem. 1993, 58, 3511. (c) Evans, D. A.; Rieger, D.
L.; Gage, J. R. Tetrahedron Lett. 1990, 31, 7099.
(26) The asymmetric desymmetrization of a bicyclic, tertiary
dialkenylcarbinol by the zirconium analog of a SAE,
employing 3.0–3.4 equivalents each of Zr(i-PrO)4, D-(–)-
diisopropyl tartrate, and t-BuOOH is described in: Spivey,
A. C.; Woodhead, S. J.; Weston, M.; Andrews, B. I. Angew.
Chem. Int. Ed. 2001, 40, 769; Angew. Chem. 2001, 113, 791.
(21) Moreover, tert-butyldimethylsiloxy groups do not withstand
prolonged exposure to Red-Al®: Berkenbusch, T. PhD
Dissertation; Universität Freiburg: Germany, 2002.
Synlett 2003, No. 12, 1813–1816 © Thieme Stuttgart · New York