1,2-diol derivative 6 were unambiguously determined to be S
and R, respectively. On the other hand, a 1H NMR decoupling
experiment with compound 3 showed trans diaxial coupling
(8.2 Hz) between H1 and H2 and thus the C1 and C2
configurations of 3 were assigned as S and S, respectively.
Epoxidation of 6 with MCPBA in CH2Cl2 afforded trans-
epoxide 13 {Rf = 0.30 (silica gel, hexane2EtOAc, 10:1); [a]D
2126.9 (c 0.11)} along with its cis isomer {Rf = 0.11, [a]D
2112.0 (c 0.1)} (trans:cis = ca. 7:3) (Scheme 2). Epoxidation
in other solvents gave poorer results. Diaxial opening of the
epoxide ring of 13 with PhSeNa gave exclusively hydrox-
yselenide 14, whereupon oxidation with 30% H2O2 followed by
elimination provided allylic alcohol 15 {[a]D + 3.0 (c 0.2)}.
Dihydroxylation of 15 occurred on the opposite face to the
allylic hydroxy group to afford exclusively triol 16 {[a]D 250.5
(c 0.11)} in 92% yield. Hydrogenolysis of 16 provided muco-
quercitol 1, of which the spectroscopic data and physical
properties were identical with those of authentic material.
Further characterization of 1 was performed via transformation
to the known pentaacetate 17.9
hexane–CHCl3–EtOAc, 20:5:1); [a]D 222.3 (c 0.74)} along
with cis-epoxide {Rf = 0.35; [a]D 233.2 (c 0.80)} (trans:cis =
3:2). Diaxial opening of the epoxide ring in 19 with PhSeNa
afforded exclusively hydroxyselenide 20, which turned out to
be a mixture of two rotational isomers (3:2) about one of the
single bonds in the OTBDPS group. The mixture of two stable
atropisomers 20 was separated by flash chromatography, and
each was converted into allylic alcohol 21, which was also a
stable and separable mixture of atropisomers (3:2). Evidence for
the atropisomerism in compounds 20 and 21 could be readily
obtained by removal of their TBDPS groups. Thus, treatment of
each atropisomer of 20 with TBAF gave the diol 22 which did
not show any atropisomerism. Diol 23 {[a]D +23.0 (c 0.10)},
obtained from both atropisomers of 21 by deprotection with
TBAF, also showed no atropisomerism.
Dihydroxylation of 23 followed by hydrogenolysis of the
resultant 24 {[a]D 2 68.1 (c 0.32)} with Pd(OH)2-C (Degussa
type) in the presence of a trace amount of conc. HCl gave
D
-chiro-inositol 2, the physical properties of which are identical
with those of authentic 2.10 Perbenzoate 2511 was prepared for
further characterization of 2. A similar synthesis starting with
the (1R,2R)-diasteromer of 3 would provide -chiro-inositol.
Protection of the hydroxy group in 15 with the sterically
demanding TBDPS group and subsequent epoxidation of the
resulting TBDPS ether 18 {[a]D +17.8 (c 1.1)} with MCPBA
afforded the desired trans-epoxide 19 {Rf = 0.40 (silica gel,
L
The development of the highly diastereoselective oxyselenen-
ylation of cyclohexene with various chiral alcohols including
hydrobenzoin derivatives is now in progress.
This work was supported by a grant from Basic Research
Institute Program (BSRI-97-3422), Ministry of Education,
Korea. Support from OCRC-KOSEF is also acknowledged.
OH
O
O
O
Ph
Ph
PhSe
O
O
Ph
Ph
O
O
Ph
Ph
i
ii
Notes and References
14
6
13
† E-mail: kwan@alchemy.yonsei.ac.kr
iii
‡ Selected data for 3: colourless glass (Found: C, 69.16; H, 6.42.
C26H28O2Se requires C, 69.17; H, 6.25%); Rf = 0.27 (silica gel, hexane–
EtOAc, 7:1); [a]D +4.2 (c 0.55, CH2Cl2); dH(500 MHz; CDCl3) 1.20–1.36
(2 H, m), 1.39–1.52 (2 H, m), 1.53–1.63 (1 H, m), 1.65–1.73 (1 H, m),
2.02–2.10 (1 H, m), 2.12–2.19 (1 H, m), 3.31–3.37 (1 H, m), 3.39–3.45 (2
H, m), 4.37 and 4.62 (2 H, ABq, J 8.1), 6.96–7.01 (2 H, m), 7.07–7.22 (11
H, m), 7.36–7.40 (2 H, m). For (1R,2R)-diastereomer of 3: white solid, mp
60–62 °C; Rf = 0.37 (silica gel, hexane–EtOAc, 7:1); [a]D 279.5 (c 1.48,
CH2Cl2); dH(500 MHz; CDCl3) 1.02–1.14 (2 H, m), 1.16–1.28 (1 H, m),
1.41–1.62 (3 H, m), 1.64–1.72 (1 H, m), 2.14–2.21 (1 H, m), 3.21–3.28 (1
H, m), 3.44–3.50 (1 H, m), 4.26 and 4.68 (2 H, ABq, J 8.7), 4.72–4.80 (1 H,
s), 6.92–6.94 (2 H, m), 6.92–7.02 (2 H, m), 7.12–7.19 (6 H, m), 7.29–7.32
(3 H, m), 7.68–7.72 (2 H, m).
OH
OR
OH
O
O
Ph
Ph
RO
OR
HO
HO
O
O
Ph
Ph
v
iv
RO
vi
OR
1 R = H
17 R = Ac
16
15
vii
OR
OTBDPS
O
OTBDPS
O
HO
O
O
Ph
ix
Ph
Ph
Ph
§
Unlike the first oxyselenenylation step, the intramolecular oxy-
viii
O
selenenylation proceeded in a reasonable yield only with PhSeOTf, possibly
because other selenium reagents, including N-PSP, are not reactive enough
for the intramolecular oxyselenenylation.
PhSe
Ph
O
Ph
O
20 R = TBDPS
22 R = H
19
18
1 Reviews: T. Hudlicky, D. A. Entwistle, K. K. Pitzer and A. J. Thorpe,
Chem. Rev., 1996, 96, 1195; J. J. Kiddle, Chem. Rev., 1995, 95, 2189;
T. Hudlicky and M. Cebulak, Cyclitols and Derivatives, VCH, New
York, 1993; D. C. Billington, The Inositol Phosphates—Chemical
Synthesis and Biological Significance, VCH, Weinheim, 1993.
2 T. Hudlicky and A. J. Thorpe, Chem. Commun., 1996, 1993.
3 A. Angelaud and Y. Landais, Tetrahedron Lett., 1997, 38, 1407; J. Org.
Chem., 1996, 61, 5202.
x
OR
OR
OH
O
RO
OR
OR
HO
O
O
Ph
HO
HO
Ph
xii
xiii
RO
Ph
O
Ph
4 D. Liotta, G. Zima and M. Saindane, J. Org. Chem., 1982, 47, 1258.
5 K. S. Kim, H. B. Park, J. Y. Kim, Y. H. Ahn and I. H. Jeong,
Tetrahedron Lett., 1996, 37, 1249.
6 J. M. Mato, K. L. Kelly, A. Alber, L. Jarett, B. E. Corkey, J. A. Cashel
and D. Zopf, Biochem. Biophys. Res. Commun., 1987, 146, 764; J.
Larner, L. C. Huang, C. F. W. Schwartz, A. S. Oswald, T. Y. Shen, M.
Kinter, G. Tang and K. Zeller, Biochem. Biophys. Res. Commun., 1988,
151, 1416.
7 H. Paulsen and O. Brauer, Chem. Ber., 1977, 110, 331.
8 H. Z. Sable, K. A. Powell, H. Katchian, C. B. Niewoehner and S. B.
Kadlec, Tetrahedron, 1970, 26, 1509.
9 G. E. McCasland, Adv. Carbohydr. Chem. Biochem., 1965, 20, 11.
10 Carbohydrates, ed. P. M. Collins, Chapman and Hall, New York, 1987,
p. 289.
OR
OH
21 R = TBDPS
23 R = H
2 R = H
xi
24
xiv
25 R = Bz
Scheme 2 Reagents and conditions: i, MCPBA, NaHCO3, CH2Cl2, reflux,
16 h, 60% of 13 and 26% of its cis isomer; ii, PhSeSePh, NaBH4, EtOH,
reflux, 4 h, 95%; iii, 30% H2O2, THF–EtOH, room temp., then reflux, 6 h,
96%; iv, K2OsO4H2O (cat.), NMO, acetone–H2O, reflux, 20 h, 92%; v, H2,
Pd(OH)2 (cat.), conc. HCl (trace), EtOH, 15 psi, room temp., 1 h, 93%; vi,
Ac2O, pyridine, room temp., 12 h, 85%; vii, TBDPSCl, imidazole, DMF,
reflux, 14 h, 87%; viii, MCPBA, NaHCO3, CH2Cl2, reflux, 20 h, 51% of 19
and 34% of its cis isomer; ix, PhSeSePh, NaBH4, BunOH, reflux, 24 h, 83%
(a mixture of two atropisomers, 3:2); x, NaIO4, NaHCO3, MeOH–H2O,
room temp., 10 min, then 90 °C, 48 h, 90% (a mixture of two atropisosmers,
3:2); xi, Bun4NF, THF, room temp., 5 h, 92%; xii, K2OsO4H2O (cat.),
NMO, acetone–H2O, reflux, 18 h, 87%; xiii, H2, Pd(OH)2 (cat.), conc. HCl
(trace), EtOH, 15 psi, room temp., 1 h, 82%; xiv, BzCl, pyridine, 12 h, room
temp., 86%
11 E. A. Kobat, D. L. McDonald, C. E. Balbu and H. O. L. Fisher, J. Am.
Chem. Soc., 1953, 75, 4507.
Received in Cambridge, UK, 1st June 1998; 8/04072I
1946
Chem. Commun., 1998