K. C. Golden et al. / Tetrahedron Letters 51 (2010) 4010–4013
4013
Y.; Zeng, D.; Zablocki, J. Bioorg. Med. Chem. Lett. 2007, 17, 161; (d) Hampton, A. J.
Am. Chem. Soc. 1961, 83, 3640.
11. Additionally we have demonstrated chemoselective terminal acetonide
deprotection of 19 at room temperature for 8 h to cleanly give 20.
Subsequent microwave heating at 120 °C for 30 min then gave 21 in
excellent yield. While this particular example demonstrates the
chemoselective removal of a terminal versus internal acetonide using both
room temperature and microwave heating conditions at 100 °C, depending on
the nature of the substrates, future investigators may want to first use the
room temperature conditions to selectively remove a terminal acetonide in the
presence of an internal acetonide, albeit with increased reaction times.
12. (a) Sodium diethylamide/HMPA, benzene, reflux, 12 h, Melis, S.; Piras, P.;
Pumitallo, A. J. Heterocycl. Chem. 1983, 20, 1413–1414.; (b) MeOH/HCl, 55 °C,
30 min, Meltzer, P. Bioorg. Med. Chem. Lett. 2003, 13, 4133–4137.; (c) AcOH/6 N
HCl, reflux, 2 h, Pak, J. J.; Mayo, J. L.; Shurdha, E. Tetrahedron Lett. 2006, 47, 233.;
4
5
.
.
Burke, S. D.; Jung, K. W.; Phillips, J. R.; Perri, R. E. Tetrahedron Lett. 1994, 35, 703.
(a) Kim, K. s.; Song, Y. H.; Lee, B. H.; Hahn, C. S. J. Org. Chem. 1986, 51, 404; (b)
Iwata, M.; Ohrui, H. Bull. Chem. Soc. Jpn. 1981, 54, 2837; (c) Vijayasaradhi, S.;
Singh, J.; Aidhen, I. S. Synlett 2000, 1, 110; (d) Swamy, N. R.; Venkateswarlu
Tetrahedron Lett. 2002, 43, 7549; (e) Pfrengle, F.; Dekaris, V.; Schefzig, L.;
Zimmer, R.; Reissig, H.-U. Synlett 2008, 19, 2965; (f) Procopio, A.; Gaspari, M.;
Nardi, M.; Oliverio, M.; Romeo, R. Tetrahedron Lett. 2008, 49, 1961; (g) Yadav, J.
S.; Reddy, B. V. S.; Reddy, K. S. Chem. Lett. 2001, 430.
6
.
(a) Ohgi, T.; Kondo, T.; Goto, T. Tetrahedron Lett. 1977, 4051; (b) Mahender, G.;
Ramu, R.; Ramesh, C.; Das, B. Chem. Lett. 2004, 734; (c) Leblanc, Y.;
Fitzsimmons, B. J.; Adams, J.; Perez, F.; Rokach, J. J. Org. Chem. 1986, 51, 789;
(
9
d) Rawal, G. K.; Rani, S.; Kumar, A.; Vankar, Y. D. Tetrahedron Lett. 2006, 47,
117; (e) Park, K. H.; Yoon, Y. J.; Lee, S. G. Tetrahedron Lett. 1994, 35, 9737; (f)
(d) TsOHÁH
2
O, CH
3
CN/H
2
O, 80 °C, 6 h; Bernini, R.; Cacchi, S.; Fabrizi, G.; Filisti,
E. Org. Lett. 2008, 10, 3457.; (e) TFA/triisopropylsilane/H
2
O, rt, 30 min; Liu, Z.;
Yadav, J. S.; Chander, M. C.; Reddy, K. K. Tetrahedron Lett. 1992, 33, 135; (g)
Ichihara, M. U.; Sakamura, S. Tetrahedron Lett. 1977, 18, 3473.
Hu, B.; Messersmith, P. B. Tetrahedron Lett. 2008, 49, 5519–5521.
13. (R)-3-(benzyloxy)propane-1,2-diol (2): A Biotage microwave process tube
with stir bar was charged with (S)-4-(benzyloxymethyl)-2,2-dimethyl-1,3-
dioxolane (1, 222 mg, 1.0 mmol) in acetonitrile:water (5 mL, 9:1 v/v) and
7
8
9
.
.
.
Gregg, B. T.; Golden, K. C.; Quinn, J. F. J. Org. Chem. 2007, 72, 5890.
Giri, S. K.; Verma, M.; Kartha, K. P. J. Carbohydr. Chem. 2008, 27, 464.
Under the conditions reported, the yields for the acetonide deprotection for a
simple sugar possessing both an internal and terminal acetonide were reported
to be 70% and 75%. While the authors do not explain the relatively low yield,
based on their other data, it is likely that this is due to the partial, non-selective
deprotection of both the internal and terminal acetonide groups.
0. (a)For additional reports on microwave methods: Microwave Methods in
Organic Synthesis; Larhead, M. O. K., Ed.; Springer: Berlin, 2006; (b) Quinn, J.
F.; Razzano, D. A.; Golden, K. C.; Gregg, B. T. Tetrahedron Lett. 2008, 49, 6137;
3
In(OTf) (1.0 mol%). The resulting mixture was heated under microwave
conditions at 100 °C for 5 min after which time the solvents were removed
under vacuum. The crude product was taken up into dichloromethane (10 mL)
and treated with PS-trisamine resin (30 mg) for 5 min to remove residual
indium salts, filtered and concentrated to dryness under vacuum to give (R)-3-
1
(benzyloxy)propane-1,2-diol (2, 0.170 g, 93%): 1H NMR (300 MHz, CDCl
3
) d
7.38–7.28 (5H, m), 4.53 (2H, s), 3.87–3.80 (1H, m), 3.69–3.47 (4H, m), 2.89 (2H,
Br s); 13C NMR (75 MHz, CDCl
) d 137.7, 128.5, 127.9, 127.8, 73.6, 71.8, 70.8,
64.1; APCI MS m/z 183.1 [M + 1] ; HPLC 98.3% (220 nm, AUC).
14. (3S,4S)-3,4-dihydroxydihydrofuran-2(3H)-one (6): Biotage microwave
3
+
(
c) Pabba, C.; Wang, H.-J.; Mulligan, S. R.; Chen, Z.-J.; Stark, T. M.; Gregg, B.
T. Tetrahedron Lett. 2005, 46, 7553; (d) Sauer, D. R.; Kalvin, D.; Phelan, K. M.
Org. Lett. 2003, 5, 4721; (e) Wang, Y.; Sauer, D. R. Org. Lett. 2004, 6, 2793; (f)
Wang, Y.; Miller, R. L.; Sauer, D. R.; Djuric, S. W. Org. Lett. 2005, 7, 925; (g)
Gregg, B. T.; Tymoshenko, D. O.; Razzano, D. A.; Johnson, M. R. J. Comb.
Chem. 2007, 9, 507; (h) Wang, H.-J.; Keilman, J.; Pabba, C.; Chen, Z.-J.; Gregg,
B. T. Tetrahedron Lett. 2005, 46, 2631; (i) Tymoshenko, D. O.; Gregg, B. T.;
Hirsch, M. J.; Butcher, J. L. Lett. Drug Des. Discov. 2008, 5, 43; (j) Gregg, B. T.;
Golden, K. C.; Quinn, J. F.; Tymoshenko, D. O.; Earley, W. G.; Maynard, D. A.;
Razzano, D. A.; Rennells, W. M.; Butcher, J. J. Comb. Chem. 2007, 9, 1036; (k)
Yoon, D. S.; Han, Y.; Stark, T. M.; Haber, J. C.; Gregg, B. T.; Stankovich, S. B.
Org. Lett. 2004, 6, 4775; (l) Gregg, B. T.; Golden, K. C.; Quinn, J. F.; Wang, H.-
J.; Zhang, W.; Wang, R.; Wekesa, F.; Tymoshenko, D. O. Tetrahedron Lett.
A
process tube with stir bar was charged with (3aS,6aS)-2,2-dimethyl-
dihydrofuro[3,4-d][1,3]dioxol-4(3aH)-one (5, 158 mg, 1.0 mmol) in acetonitrile:
water (5 mL, 9:1 v/v) and In(OTf) (1.0 mol%). The resulting mixture was
3
heated under microwave conditions at 120 °C for 30 min after which time the
solvents were removed under vacuum. The crude product was taken up into
dichloromethane (10 mL) and treated with PS-trisamine resin (30 mg) for 5
min to remove residual indium salts, filtered and concentrated to dryness
under vacuum to give (3S,4S)-3,4-dihydroxy-dihydrofuran-2(3H)-one (6,
1
0.112g, 95%): H NMR (300 MHz, DMSO-d
6
) d 5.60 (2H, br s), 4.37 (1H, d, J =
1
2
4.7 Hz), 4.28 (1H, dd, J = 9.85 Hz, J = 3.05 Hz), 4.24–4.21 (1H, m), 4.04 (1H, d, J
= 9.8 Hz); 13C NMR (75 MHz, DMSO-d
6
) d 176.3, 71.7, 69.4, 68.3; APCI MS m/z
+
2
009, 3978–3981.
119.2 [M + 1] ; HPLC 98.2% (220 nm, AUC).