T. Saito et al. / Tetrahedron Letters 42 (2001) 57–59
59
Table 3. Epoxidation of aromatic aldehydes with arylmethyl bromides and sulfide 3/K2CO3
Run
R
R%
Solvent
MeCN
Yield [conversion] (%)
Trans:cisa
Trans ee (%)a
1
2
3
Ph
Ph
Ph
Ph
Ph
Ph
p-Tol
Ph
Ph
Ph
Ph
Ph
72 [\99]
33 [89]
84 [90]
\99
96:4
56 [S,S]
61 [S,S]
75 [S,S]
57 [S,S]
57 [S,S]
91 [S,S]
71 [S,S]
65 [S,S]
66 [S,S]
75 [S,S]
76 [S,S]
p-MeOC6H4
p-Tol
p-ClC6H4
p-NO2C6H4
Ph
82:18
81:19
95:5
4b
5c
6
\99
95:5
58 [69]
30 [\99]
47 [85]
51 [\99]
\99
80:20
77:23
77:23
76:24
79:21
76:24
7
8
9
Ph
t-BuOH
p-MeOC6H4
p-Tol
p-ClC6H4
p-NO2C6H4
10d
11
\99
a Determined by HPLC [Chiralcel OD, i-PrOH–hexane (1:30–1:200)]. The absolute configuration was assigned by comparison of the sign (−) of
specific rotation with the literature data or by assumption.3–9
b For 2 days.
c For 1 day.
d For 3 days.
6. Solladie´-Cavallo, A.; Diep-Vohuule, A.; Sunjic, A.;
Vinkovic, V. Tetrahedron: Asymmetry 1996, 7, 1783.
7. Dai, L.-X.; Lou, B.-L.; Zhang, Y.-Z. J. Am. Chem. Soc.
1988, 110, 5915; Li, A.-H.; Dai, L.-X.; Hou, X.-L.;
Huang, Y.-Z.; Li, F.-W. J. Org. Chem. 1996, 61, 489.
8. Aggarwal, V. K.; Ford, J. G.; Thompson, A.; Jones, R. V.
H.; Standen, M. C. H. J. Am. Chem. Soc. 1996, 118, 704;
Aggarwal, V. K.; Ford, J. G.; Fonquerna, S.; Adams, H.;
Jones, R. V. H.; Fieldhouse, R. J. Am. Chem. Soc. 1998,
120, 8328; Aggarwal, V. K.; Ford, J. G.; Jones, R. V. H.;
Fieldhouse, R. Tetrahedron: Asymmetry 1998, 9, 1801.
9. Julienne, K.; Metzner, P.; Henryon, V. J. Chem. Soc.,
Perkin Trans. 1 1999, 731; Julienne, K.; Metzner, P. J.
Org. Chem. 1998, 63, 4532. See also Reference 5.
10. Hayakawa, R.; Shimizu, M. Synlett 1999, 1328.
11. Imashiro, R.; Yamanaka, T.; Seki, M. Tetrahedron:
Asymmetry 1999, 10, 2845.
The present study demonstrates the enantiomeric, one-
pot synthesis of optically active epoxides via the
Corey–Chaykovsky reaction, and makes this process
promising because of the easy and simple but efficient
preparation of the chiral sulfide with good crystallinity
and the feasible introduction of a variety of substituents
to the thiane ring to tune up the stereoselectivities by
further manipulation.
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.