7608
Y. Demizu et al. / Tetrahedron Letters 48 (2007) 7605–7609
BzCl (1.2 equiv)
DMAP (1.0 equiv)
3529–3532; (b) Mizuta, S.; Sadamori, M.; Fujimoto, T.;
OH
OBz
OTs
Yamamoto, I. Angew. Chem., Int. Ed. 2003, 42, 3383–
3385; (c) Vedejs, E.; Daugulis, O.; Tuttle, N. J. Org. Chem.
2004, 69, 1389–1392; (d) Mazet, C.; Ko¨hler, V.; Pfaltz, A.
Angew. Chem., Int. Ed. 2005, 44, 4888–4891; (e) Yamada,
S.; Misono, T.; Iwai, Y.; Masumizu, A.; Akiyama, Y. J.
Org. Chem. 2006, 71, 6872–6880; (f) Nakamura, D.;
Kakiuchi, K.; Koga, K.; Shirai, R. Org. Lett. 2006, 8,
6139–6142; (g) Arai, T.; Mizukami, T.; Yanagisawa, A.
Org. Lett. 2007, 9, 1145–1147.
Et3N (1.5 equiv)
CH2Cl2, rt, 24 h
OTs
ð8Þ
6ap
97% ee
7
84 % yield, 97% ee
[α]27D −12.2 (
c
1.0, CHCl3)
p
-TsCl (1.2 equiv)
OBz
OH
DMAP (1.0 equiv)
OBz
OTs
2. For (S,S)-Ph-BOX: (a) Corey, E. J.; Imai, N.; Zhang, H.-
Y. J. Am. Chem. Soc. 1991, 113, 728–729; A recent review
of chiral bis(oxazoline) ligands: (b) Desimoni, G.; Faita,
G.; Jørgensen, K. A. Chem. Rev. 2006, 106, 3561–3651.
3. (a) Matsumura, Y.; Maki, T.; Murakami, S.; Onomura, O.
J. Am. Chem. Soc. 2003, 125, 2052–2053; (b) Matsumura,
Y.; Maki, T.; Tsurumaki, K.; Onomura, O. Tetrahedron
Lett. 2004, 45, 9131–9134; (c) Matsumura, Y.; Onomura,
O.; Demizu, Y. Yuki Gosei Kagaku Kyokaishi 2007, 65,
216–225.
Et3N (1.5 equiv)
CH2Cl2, rt, 24 h
ð9Þ
8
7
93% ee
84% yield, 93% ee
[α]27D -11.6 (
1.0, CHCl3)
c
It is convenient for chemical transformations of com-
pound 7 into optically active compounds 9–11 that
tosyloxy substituent of compound 7 is a good leaving
group for SN2 reaction and E2 reaction. At first, 7 was
treated with NaN3 to obtain the azide compound 9 with
complete stereoinversion, followed by reduction and
benzoylation to afford the optically active vic-amino
alcohol 10 (Eq. 10).12,14 Also 7 was treated with DBU
to obtain the optically active a,b-unsaturated alcohol
derivative 11 in good yield without any loss of the opti-
cal purity of 7 (Eq. 11).15
´
4. Edin, M.; Martın-Matute, B.; Ba¨ckvall, J.-E. Tetrahedron:
Asymmetry 2006, 17, 708–715.
5. Matsumoto, K.; Mitsuda, M.; Ushijima, N.; Demizu, Y.;
Onomura, O.; Matsumura, Y. Tetrahedron Lett. 2006, 47,
8453–8456.
6. Regioselective sulfonylation of vic-diols catalyzed by tin
compounds: (a) Bucher, B.; Curran, D. P. Tetrahedron
Lett. 2000, 41, 9617–9621; (b) Martinelli, M. J.; Vaidya-
nathan, R.; Pawlak, J. M.; Nayyar, N. K.; Dhokte, U. P.;
Doecke, C. W.; Zollars, L. M. H.; Moher, E. D.; Khau, V.
NaN3 (2.0 equiv)
15-crown-5 (0.1 equiv)
DMF, 90 oC , 12 h
OBz
OTs
OBz
N3
OBz
1) H2, Pd-C, MeOH
Bz
2) BzCl (1.2 equiv)
Et3N (2.0 equiv)
DMAP (0.2 equiv)
CH2Cl2, rt, 12 h
N
H
ð10Þ
ð11Þ
7
9
10
97% yield
OBz
85% yield, 97% ee
97% ee
DBU (2.0 equiv)
DMF, 120 oC, 18 h
7
11
97% ee
80% yield, 97% ee
V.; Kosmrlj, B. J. Am. Chem. Soc. 2002, 124, 3578–
3585.
The results shown in this Letter are practical methods
for preparation of optically active monotosylated deriv-
atives from meso-vic-diols. Asymmetric monotosylation
method has generality for various meso-vic-diols and is
superior to monobenzoylation or monocarbamoylation
method. The mechanistic study of this monotosylation
and its application to a kinetic resolution of dl-vic-diols
are now under investigation.
7. A typical procedure for asymmetric monotosylation:
Under an aerobic atmosphere, a solution of Cu(OTf)2
(18.1 mg, 0.05 mmol) and (R,R)-Ph-BOX (16.7 mg,
0.05 mmol) in CH2Cl2 (2 mL) was stirred for 10 min. Into
the solution were added meso-1a (0.5 mmol), K2CO3
(103.7 mg, 0.75 mmol), and p-TsCl 5p (114.4 mg,
0.6 mmol). After being stirred for 12 h at rt, the solution
was poured in water and extracted with AcOEt
(20 mL · 3). The combined organic layer was dried over
MgSO4 and the solvent removed under reduced pressure.
The residue was purified by silica gel column chromatog-
raphy (n-hexane–AcOEt = 3:1) to afford (1S,2R)-6ap (94%
Acknowledgments
This work was in part supported by a Grant-in-Aid for
Scientific Research (B) (17350051) from Japan Society
for the Promotion of Science.
19
yield, 97% ee) as a colorless oil. ½aꢁD ꢀ8.1 (c 1.0, CHCl3).
IR (neat) 3530, 2942, 1599, 1356, 1175 cmꢀ1 1H NMR
.
(300 MHz, CDCl3) d 7.82 (d, J = 8.7 Hz, 2H), 7.35 (d,
J = 7.8 Hz, 2H), 4.68–4.58 (m, 1H), 3.88–3.78 (m, 1H),
2.45 (s, 3H), 2.10–1.20 (m, 9H). 13C NMR (75 MHz,
CDCl3) d 144.6, 134.0, 129.7, 127.5, 83.0, 68.8, 30.1, 27.5,
21.5(2C), 20.6. MS [LR-FAB(+)]: m/z 271 [M+H]+. The
optical purity of 6ap was determined by chiral HPLC:
Daicel Chiralcel OJ-H column (4.6 mm B, 250 mm), n-
References and notes
1. Representative literatures for nonenzymatically asymmet-
ric monobenzoylation of meso-vic-diols: (a) Oriyama, T.;
Imai, K.; Hosoya, T.; Sano, T. Tetrahedron Lett. 1998, 39,