A. Aravind et al. / Tetrahedron Letters 46 (2005) 2965–2968
2967
2. For reductive cleavage, see: (a) Wang, C. C.; Luo, S. Y.;
Shie, C. R.; Hung, S. C. Org. Lett. 2002, 4, 847–849; (b)
Watanabe, S.; Sueyoshi, T.; Ichihara, M.; Uehara, C.;
Iwamura, M. Org. Lett. 2001, 3, 255–257; (c) Debenham,
S. D.; Toone, E. J. Tetrahedron: Asymmetry 2000, 11, 385–
387; (d) Sakagami, M.; Hamana, H. Tetrahedron Lett.
2000, 41, 5547–5551; (e) Chandrasekhar, S.; Reddy, Y. R.;
Reddy, C. R. Chem. Lett. 1998, 1273–1274; (f) Binkley, R.
W.; Goewey, G. S.; Johnston, J. C. J. Org. Chem. 1984,
49, 992–996; (g) Takano, S.; Akiyama, M.; Sato, S.;
Ogasawara, K. Chem. Lett. 1983, 1593–1596; (h) Liptak,
A.; Imre, J.; Harangi, J.; Nanasi, P. Tetrahedron 1982, 38,
3721–3727; (i) Peters, U.; Bankova, W.; Welzel, P.
Tetrahedron 1987, 43, 3803–3816.
of pTSA in dry acetone (5 mL). The resultant mixture
was allowed to stir for 5 h at room temperature. The
mixture was then diluted with EtOAc (20 mL), washed
with a saturated solution of NaHCO3 (2 · 10 mL), dried
over anhydrous Na2SO4 and concentrated under re-
duced pressure to yield a crude compound, which was
purified by column chromatography on silica gel (gradi-
ent elution with 15–25% EtOAc in hexane) to give pure
25
D
dimesylate 29 (3.1 g, 70% overall yield). ½aꢀ +28.6 (c
1.0, CHCl3); IR (neat): 1356, 1177 cmꢁ1
;
1H NMR
(400 MHz, CDCl3) d 1.33 (s, 6H), 2.98 (s, 6H), 3.65
(dd, J = 7.3, 11.2 Hz, 2H), 3.79 (dd, J = 3.4, 11.7 Hz,
2H), 4.27 (d, J = 4.8 Hz, 2H), 4.47 (AB quartet,
J = 11.7 Hz, 4H), 4.78–4.82 (m, 2H), 7.18–7.28 (m,
10H); 13C NMR (100 MHz, CDCl3) d 27.0, 38.5, 68.6,
73.2, 76.4, 80.2, 111.0, 127.6, 127.7, 128.3, 137.1; MS
(EI) m/z (relative intensity, %) 558 (32) (M+), 557 (10),
467 (23), 379 (15), 181 (100), 111 (20), 91 (60). HRMS
(ESI) calcd for C25H34O10S2Na (M+Na)+: 581.1491;
found: 581.1489.
3. For oxidative cleavage, see: (a) Hanessian, S. Org. Synth.
1986, 65, 243, and references cited therein; (b) Chretien,
F.; Khaldi, M.; Chapleur, Y. Synth. Commun. 1990, 20,
1589–1596; (c) Sueda, T.; Fukuda, S.; Ochiai, M. Org.
Lett. 2001, 3, 2387–2390.
4. Balakumar, V.; Aravind, A.; Baskaran, S. Synlett 2004,
647–650.
5. (a) Guindon, Y.; Girard, Y.; Berthiaume, S.; Gorys, V.;
Lemieux, R.; Yoakim, C. Can. J. Chem. 1990, 68, 897–
902; (b) Seiki, S.; Kuroda, A.; Tanaka, K.; Kimura, R.
Synlett 1996, 231–233; (c) Zheng, B.-Z.; Yamauchi, M.;
Dei, H.; Kusaka, S.; Matsui, K.; Yonemitsu, O. Tetrahe-
dron Lett. 2000, 41, 6441–6445.
6. (a) Babjak, M.; Kapitan, P.; Gracza, T. Tetrahedron Lett.
2002, 43, 6983–6985; (b) Chandrasekhar, M.; Raina, S.;
Singh, V. K. Tetrahedron Lett. 2000, 41, 4969–4971; (c)
Hale, K. J.; Jogiya, N.; Manaviazar, S. Tetrahedron Lett.
1998, 39, 7163–7166; (d) Cere, V.; Peri, F.; Pollicino, S.
Tetrahedron Lett. 1997, 38, 7797–7800; (e) Defoin, A.;
Brouillard-Poichet, A.; Streith, J. Helv. Chim. Acta 1991,
74, 103–109; (f) Jurczak, J.; Pikul, S.; Bauer, T. Tetrahe-
dron 1986, 42, 447–488.
7. (a) Masaki, Y.; Arasaki, H.; Itoh, A. Tetrahedron Lett.
1999, 40, 4829–4832; (b) Chen, Y.; Li, X.; Tong, S.-K.;
Choi, M. C. K.; Chan, A. S. C. Tetrahedron Lett. 1999, 40,
957–960; (c) Gryko, D. T.; Piatek, P.; Jurczak, J. Synthesis
1999, 336–340; (d) Li, W.; Zhang, Z.; Xiao, D.; Zhang, X.
Tetrahedron Lett. 1999, 40, 6701–6704; (e) Marotta, E.;
Baravelli, M.; Maini, L.; Righi, P.; Rosini, G. J. Org.
Chem. 1998, 63, 8235–8246; (f) Gauzy, L.; Merrer, Y. L.;
Depezay, J. C. Synlett 1998, 402–404; (g) Byung, T. C.;
Yu, S. C. Tetrahedron: Asymmetry 1998, 9, 1489–1492; (h)
Giese, B.; Muller, S. N.; Wyss, C.; Steiner, H. Tetrahe-
dron: Asymmetry 1996, 7, 1261–1262.
Experimental procedure for oxidative cleavage of 2,5-di-
with
mesylated-1,3:4,6-di-O-benzylidene-D-mannitol
1
NBS. To a solution of dibenzylidene acetal 1 (1.03 g,
2 mmol) in dry CCl4 (60 mL) was added N-bromosuc-
cinimide (854 mg, 4.8 mmol) and the resultant mixture
was refluxed under a nitrogen atmosphere in the pres-
ence of incandescent light for 30 min. After completion
of the reaction, as indicated by TLC (ca. 1 h), the reac-
tion mixture was cooled to room temperature and di-
luted with 20 mL CH2Cl2. The organic layer was then
washed with saturated aqueous NaHCO3 solution
(2 · 30 mL), dried over anhydrous Na2SO4 and concen-
trated under reduced pressure to yield the crude com-
pound, which was purified by column chromatography
on silica gel (gradient elution with 20–30% EtOAc in
hexane) to furnish pure bromomesylate 3 as a white
25
foamy solid (1.2 g, 90% yield). ½aꢀ ¼ þ46:4 (c 1.0,
D
1
CHCl3); IR (KBr): 1729, 1361, 1255 cmꢁ1; H NMR
(400 MHz, CDCl3) d 3.04 (s, 6H), 3.66 (dd, J = 12.2,
11.7 Hz, 2H), 3.88 (dd, J = 12.2, 11.7 Hz, 2H), 5.24
(m, 2H), 5.81 (d, J = 5.9 Hz, 2H), 7.39–7.58 (m, 4H),
8.00–8.02 (m, 6H); 13C NMR (100 MHz, CDCl3) d
30.1, 39.0, 69.0, 128.9, 130.2, 134.2, 165.3; HRMS
(FAB) calcd for C22H24O10S2Br2Na (M+Na)+
692.9075; found 692.9057.
8. Lohray, B. B.; Baskaran, S.; Rao, B. S.; Reddy, B. Y.;
Rao, I. N. Tetrahedron Lett. 1999, 40, 4855–4856.
9. Aravind, A.; Baskaran, S. Tetrahedron Lett. 2005, 46,
743.
10. (a) Winn, C. L.; Goodman, J. M. Tetrahedron Lett. 2001,
42, 7091–7093; (b) Baggett, N.; Stribblehill, P. J. Chem.
Soc., Perkin Trans. 1 1977, 1123–1126.
Acknowledgements
11. Reddy, P. G.; Pratap, T. V.; Kishore Kumar, G. D.;
Mohanty, S. K.; Baskaran, S. Eur. J. Org. Chem. 2002,
3740–3743.
We thank CSIR, New Delhi, for the financial support,
SAIF-IIT Madras for spectral data and the DST-FIST
program for NMR facilities. A.A., S.K.M. and T.V.P.
thank CSIR, New Delhi, for research fellowships.
12. (a) Hulten, J.; Bonham, N. M.; Nillroth, U.; Hansson, T.;
Zuccarello, G.; Bouzide, A.; Aqvist, J.; Classon, B.;
Danielson, U. H.; Karlen, A.; Kvarsnstrom, I.; Samuels-
son, B.; Hallberg, A. J. Med. Chem. 1997, 40, 885–897; (b)
Kempf, D. J.; Codacovi, L.; Wang, X. C.; Kohlbrenner,
W. E.; Saldivar, A.; Vasavanonda, S.; Marsh, K. C.;
Brzant, P.; Sham, H. L.; Green, B. E.; Betebenner, D. A.;
Erickson, J.; Norbeck, D. W. J. Med. Chem. 1993, 36,
320–330; (c) Zuccarello, G.; Bouzide, A.; Kvarnstrom, I.;
Niklasson, G.; Svenssson, S. C. T.; Brisander, M.;
Danielsson, H.; Nillroth, U.; Karlen, A.; Hallberg, A.;
References and notes
1. (a) Greene, T. W.; Wuts, P. G. M. Protecting Groups in
Organic Synthesis; John Wiley & Sons: New York, 1999;
(b) Hanessian, S. Preparative Carbohydrate Chemistry;
Marcel Dekker: New York, 1997; (c) Kocienski, P. J.
Protecting Groups; George Thieme: Stuttgart, 1994.