G. Wu et al. / Tetrahedron Letters 50 (2009) 427–429
429
OH
O
O
Cat 1
(S,S)-
KOH aq
CH2Br
CH2Br
(R)
ee = 91%
(R)
CHCl3
( quant.)
HCOOH:Et3N = 5:2,
DMF, rt.
4
5
3
(30% yield)
SO2Ph
SPh
PhSH
H2O2, AcOH
CH2OH
CH2OH
(S)
(S)
NaBH4, EtOH,
(38% yield)
THF, reflux, 9 h
(62% yield)
ee = 89%
ee = 89%
6
7
Scheme 1.
2. Peach, P.; Cross, D. J.; Kenny, J. A.; Mann, I.; Houson, I.; Campbell, L.; Walsgrove,
T.; Wills, M. Tetrahedron 2006, 62, 1864–1876.
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including 2-naphthylacetaldehyde, the reactions gave good yields
(83–92%) and high selectivities (83–90% ee, entries 1, 3, 4, 5, 7, 8,
9, and 11). The reaction seems to be insensitive to the electronic
nature of the substituents. However, the steric feature of the sub-
strates plays an important role. Thus, ortho-substitution including
electron-donating and electron-withdrawing substitution, resulted
in lower yield and dramatically decreased enantioselectivity (en-
tries 2, 6, and 10). 3-Substituted 2-sulfonylpropanals also under-
went this reaction smoothly (entries 13–15).
The absolute configuration of the product 2s was determined
according to the procedure shown in Scheme 1. Enantioselective
transfer hydrogenation of 2-bromo-1-phenylethanone 3 by using
[RuCl2(p-cymene)](S,S)-TsDPEN as the catalyst provided (R)-2-bro-
mo-1-phenylethanol 4 according to the known procedure,25 which
was then converted into the (R)-2-phenyloxirane 5 by treatment
with aqueous KOH.26 Easy ring-opening of this compound with
PhSH as the nucleophile27 resulted in the formation of the (S)-2-
phenyl-2-(phenyithio)ethanol 6, which was then oxidized with
H2O2–AcOH system to give the corresponding sulfone (S)-7 with-
out racemization.28 The retention time of this compound was
found equal to that of 2s. Based on this, together with the fact that
they have the same sign of optical rotation, the absolute configura-
tion of 2s should be (S). The configuration of compounds 2e, 2g, 2h,
2i, 2k, 2l, 2m, and 2o was assigned to (S) by analogy.
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15. (a) Solladié, G.; Fréchou, C.; Demailly, G.; Greck, C. J. Org. Chem. 1986, 51, 1912–
1914; (b) Robin, S.; Huet, F.; Fauve, A.; Veschambre, H. Tetrahedron: Asymmetry
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Tetrahedron Lett. 1986, 27, 4817–4820; (d) Sato, T.; Okumura, Y.; Itai, J.;
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In conclusion, we have demonstrated that using [RuCl2(p-cyme-
ne)](S,S)-TsDPEN as the catalyst, and HCOOH/Et3N as the hydrogen
source, a variety of 2-sulfonyl aldehydes could be reduced to the
corresponding optically active primary alcohols with DKR in good
yields and with up to 90% ee, providing an efficient method for
the asymmetric synthesis of 2-sulfonyl primary alcohols.
17. Kiełbasin´ski, P.; Rachwalski, M.; Mikołajczyk, M.; Moelands, M. A. H.; Zwanenburg, B.;
Rutjes, F. P. J. T. Tetrahedron: Asymmetry 2005, 16, 2157–2160.
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19. For reviews, see: (a) Servi, S. Synthesis 1990, 1–25; (b) Csuk, R.; Glänzer, B. I.
Chem. Rev. 1991, 91, 49–97; (c) Roberts, S. M. J. Chem. Soc., Perkin Trans. 1 1999,
1–21; (d) Crumbie, R. L.; Deol, B. S.; Nemorin, J. E.; Ridley, D. D. Aust . J. Chem.
1978, 31, 1965–1980; (e) Gotor, V.; Rebolledo, F.; Liz, R. Tetrahedron:
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2095–2098.
Supplementary data
22. (a) Bertus, P.; Phansavath, P.; Ratovelomanana-Vidal, V.; Genêt, J.-P.; Touati, A.
R.; Homri, T.; Ben Hassine, B. Tetrahedron Lett. 1999, 40, 3175–3178; (b) Bertus,
P.; Phansavath, P.; Ratovelomanana-Vidal, V.; Genêt, J. P.; Touati, A. R.; Homri,
T.; Ben Hassine, B. Tetrahedron: Asymmetry 1999, 10, 1369–1380.
23. Zhang, H.-L.; Hou, X.-L.; Dai, L.-X.; Luo, Z.-B. Tetrahedron: Asymmetry 2007, 18,
224–228.
Supplementary data associated with this article can be found, in
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