N. B. Kalamkar et al. / Tetrahedron Letters 51 (2010) 6745–6747
6747
M.; Wang, Y.; Watts, J. Bioorg. Med. Chem. 2004, 12, 5689; (d) Guitot, K.;
Carboni, S.; Reiser, O.; Piarulli, U. J. Org. Chem. 2009, 74, 8433.
10. Babu, I. R.; Ganesh, K. N. J. Am. Chem. Soc. 2001, 123, 2079.
11. For some leading references, see: (a) Yoshitomi, Y.; Makino, K.; Hamada, Y. Org.
Lett. 2007, 9, 2457; (b) List, B.; Lerner, R. A.; Barbas, C. F. J. Am. Chem. Soc. 2000,
122, 2395.
4.14 (1H, dd, J = 7.2 and 3.5 Yz, H-4), 4.60 (1H, d, J = 3.0 Hz, H-3), 4.72–4.84 (1H,
br, NH), 4.93 (1H, d, J = 4.1 Hz, H-2), 5.08 (2H, AB quartet, J = 12.3 Yz, O-CH2Ph),
5.30 (1H, bd, J = 9.4 Yz, H-6a), 5.46 (1H, bd, J = 17.6 Yz, H-6b), 5.70ꢀ5.85 (1H,
m, H-5) 5.82 (1H, d, J = 4.1 Yz, H-1), 7.20ꢀ7.40 (5H, br s, ArꢀH); 13C NMR
(75 MHz, CDCl3) d 26.1 (CH3), 26.4 (CH3), 58.1 (C-3), 66.8 (O-CH2Ph), 78.0
(strong), 84.2 (C-2), 103.8 (C-1), 111.7, 118.5 (C-6), 128.0, 128.1, 128.4, 130.9
(Ar), 135.1 (C-5), 155.6 (NCOO). Anal. Calcd for C17H21NO5: C, 63.94; H, 6.63; N,
4.39. Found: C, 64.04; H, 6.75; N, 4.62. Data for compound (8): white solid. Mp
12. For racemic cis and trans-3-hydroxyprolines see: (a) Morita, K.; Irreverre, F.;
Sakiyama, F.; Witkop, B. J. Am. Chem. Soc. 1963, 85, 2832; (b) Sheehan, J. C.;
Whitney, J. G. J. Am. Chem. Soc. 1963, 85, 3863; (c) Wolff, J. S.; Ogle, J. D.; Logan,
M. A. J. Biol. Chem. 1966, 241, 1300; (d) Sheehan, J. C.; Whitney, J. G. J. Biol.
Chem. 1963, 85, 1863; (e) Hausler, J. Liebigs. Ann. Chem. 1981, 1073.
13. For cis isomer (2S,3R) (ꢀ)-1 see: (a) Thaning, M.; Wistrand, L.-G. Acta Chem.
Scand. 1989, 43, 290; (b) Jurczak, J.; Prokopowicz, P.; Golebiowski, A.
Tetrahedron Lett. 1993, 34, 7107; (c) Sundram, H.; Golebiowski, A.; Johnson,
C. R. Tetrahedron Lett. 1994, 35, 6975; (d) Dell’Uomo, N.; Di Giovanni, M. C.;
Misiti, D.; Zappia, G.; Delle Monache, G. Tetrahedron: Asymmetry 1996, 7, 181;
(e) Sugisaki, C. H.; Carroll, P. J.; Correia, C. R. D. Tetrahedron Lett. 1998, 39, 3413;
(f) Sibi, M. P.; Christensen, J. W. Tetrahedron Lett. 1995, 36, 6213; (g) Gómez-
Vidal, J. A.; Silverman, R. B. Org. Lett. 2001, 3, 2481; Ref. 13(f) and (g) does not
describe the synthesis of the free amino acid but the protected version:
(2S,3R)-N-Boc-3-hydroxyproline methyl ester. For the enantiomer of 1 (2R,3S)
see: (h) Roemmele, R. C.; Rapoport, H. J. Org. Chem. 1989, 54, 1866; (i) Sibi, M.
P.; Christensen, J. W. Tetrahedron Lett. 1990, 31, 5689; This Letter does not
describe the synthesis of the free amino acid but the protected version:
(2R,3S)-N-Cbz-3-hydroxyproline ethyl ester; (j) Mulzer, J.; Meier, A.;
Buschmann, J.; Luger, P. J. Org. Chem. 1996, 61, 566; (k) Cooper, J.; Gallagher,
P. T.; Knight, D. W. J. Chem. Soc., Perkin Trans. 1 1993, 1313; (l) Li, J. H.; Kang, J.
E.; Yang, M. S.; Kang, K. Y.; Park, K. H. Tetrahedron 2001, 57, 10071; (m) Gryko,
D.; Prokopowicz, P.; Jurczak, J. Tetrahedron: Asymmetry 2002, 13, 1103; For
(2R,3R)- and (2S,3S)-trans-3-hydroxyprolines see: (n) Paupardin, O.; Greck, C.;
Genet, J. P. Synlett 1998, 1279; (o) Hughes, P.; Clardy, J. J. Org. Chem. 1989, 54,
3260; (p) Herdeis, C.; Hubmann, H. P.; Lotter, H. Tetrahedron: Asymmetry 1994,
5, 119; (q) Durand, J.-O.; Larchevque, M.; Petit, Y. Tetrahedron Lett. 1998, 39,
5743; (r) Huang, P.-Q.; Huang, H.-Y. Synth. Commun. 2004, 34, 1377; (s) Sinha,
S.; Tilve, S.; Chandrasekaran, S. Arkivoc 2005, 11, 209.
86–88 °C, lit.6a mp 88–89 °C; Rf 0.5 (n-hexane/ethyl acetate = 6/4); ½a 2D0
ꢁ
ꢀ66.3°
(c 1.1, CHCl3), lit.6a
½
a 2D0
ꢁ
ꢀ62.8° (CHCl3); IR (KBr) 1710, 1270, 1078 cmꢀ1
;
1H
NMR 300 MHz (DMSO-d6) d 1.22 (3H, s, CH3), 1.40 (3H, s, CH3), 1.68ꢀ1.98 (2H,
m, H-5), 3.07ꢀ3.27 (1H, m, H-6), 4.06 (1H, d, J = 4.1 Hz, H-3), 4.66 (1H, d,
J = 3.8 Yz, H-2), 4.76ꢀ4.85 (1H, m, H-4), 5.07 (2H, AB quartet, J = 12.3 Yz, O-
CH2Ph), 5.82 (1H, d, J = 3.8 Yz, H-1), 7.20ꢀ7.42 (5H, m, ArꢀH); 13C NMR
(75 MHz, CDCl3) d 26.4 (CH3), 27.0 (C-5), 30.2 (CH3), 45.1 (C-6), 66.9 (O-CH2Ph),
67.2 (C-3), 83.1 (C-4), 84.5 (C-2), 105.9 (C-1), 111.7, 127.8, 127.9, 128.2, 128.4,
136.5 (Ar), 154.3 (NCOO). The NMR spectra of 8 showed additional signals due
to presence of rotamers (3:2). Anal. Calcd for C17H21NO5: C, 63.94; H, 6.63; N,
4.39. Found: C, 63.77; H, 6.83; N, 4.67. Data for Compound (9): viscous oil; Rf 0.5
(n-hexane/ethylacetate = 2/3); ½a D20
ꢀ14.8 (c 0.4, CHCl3); IR (KBr) 3200–3600
ꢁ
(broad) and 1695 cmꢀ1 1H NMR 300 MHz (CDCl3 + D2O) d 1.30 (3H, s, CH3),
;
1.53 (3H, s, CH3), 1.72ꢀ1.92 (2H, m, H-5), 3.69ꢀ3.86 (2H, m, H-6), 4.20 (1H, d,
J = 3.0 Hz, H-3), 4.32ꢀ4.44 (1H, m, H-4), 4.53 (1H, d, J = 3.8 Hz, H-2) 4.72ꢀ4.88
(2H, br m, NH, HDO), 5.13 (2H, AB quartet, J = 12.0 Yz, O-CH2Ph), 5.80 (1H, d,
J = 3.8 Yz, H-1), 7.20ꢀ7.50 (5H, br, ArꢀH); 13C NMR (75 MHz, CDCl3) d 26.0
(CH3), 26.3 (CH3), 29.7, 30.8 (C-3/C-5), 58.2 (C-6), 60.0 (O-CH2Ph), 67.2 (C-4),
84.5 (C-2), 103.9 (C-1), 111.9, 128.3, 128.5, 130.9, 136.0 (Ar), 155.8 (NCOO).
Anal. Calcd for C17H23NO6: C, 60.52; H, 6.87; N, 4.15. Found: C, 60.75; H, 7.02;
N, 3.95. Data for compound (10): sticky solid; yield 98%; Rf 0.5 (n-hexane/
ethylacetate = 7/3); ½a D20
ꢀ8.7 (c 0.75, CHCl3); IR (KBr) 1710, 1440, 1350 and
ꢁ
1170 cmꢀ1 1H NMR 300 MHz (CDCl3) d 1.22 (3H, s, CH3), 1.43 (3H, s, CH3),
;
1.84ꢀ2.0 (2H, m, H-5), 2.92 (3H, s, OMs), 4.10ꢀ4.33 (4H, m, H-6, H-3, H-4), 4.43
(1H, d, J = 3.8 Hz, H-2), 4.82ꢀ4.92 (1H, br, NH), 5.04 (2H, AB quartet, J = 12.5 Yz,
O-CH2Ph), 5.71 (1H, d, J = 3.8 Yz, H-1), 7.20ꢀ7.40 (5H, br m, ArꢀH); 13C NMR
(75 MHz, CDCl3) d 26.0 (CH3), 26.3 (CH3), 28.3 (C-5), 37.2 (C-3), 57.9 (OMs),
66.8 (O-CH2Ph), 67.2 (C-6), 74.7 (C-4), 84.6 (C-2), 103.7 (C-1), 112.0, 128.2,
128.4, 128.6, 128.8, 130.9, 135.9 (Ar), 155.7 (NCOO). Anal. Calcd for
14. Kalamkar, N. B.; Kasture, V. M.; Dhavale, D. D. J. Org. Chem. 2008, 73, 3619.
15. (a) Vyavahare, V. P.; Chattopadhyay, S.; Puranik, V. G.; Dhavale, D. D. Synlett
2007, 559; (b) Chaudhari, V. D.; Ajish Kumar, K. S.; Dhavale, D. D. Tetrahedron
Lett. 2004, 45, 8363.
16. Chaudhari, V. D.; Ajish Kumar, K. S.; Dhavale, D. D. Org. Lett. 2005, 7, 5805.
17. (a) Karanjule, N. S.; Markad, S. D.; Shinde, V. S.; Dhavale, D. D. J. Org. Chem.
2006, 71, 4667; (b) Dhavale, D. D.; Jachak, S. M. Molecules 2005, 10, 893.
18. We tried the hydroborationꢀoxidation with olefin 6 to get an alcohol 9 using
9-BBN and BH3:DMS, however better results were obtained with NaBH4/I2 to
give alcohol 8. Hydroboration using NaBH4/I2 conditions see: Kanth, J. V. B.;
Bhanu Prasad, A. S.; Periasamy, M. Tetrahedron 1994, 48, 6411.
C
18H25O8NS: C, 52.04; H, 6.07; N, 3.37. Found: C, 52.25; H, 5.92; N, 3.62.
Data for compound (11): viscous oil: Rf 0.5 (CHCl3/MeOH = 7/3); ½a D20
ꢀ52.19 (c
ꢁ
1.77, CHCl3); IR (KBr) 3600–2800 (br), 1709, 1680 cmꢀ1 1H NMR (300 MHz,
;
CDCl3) d 1.85–2.20 (2H, m, H-4), 3.40–3.56 (1H, m, H-5a), 3.56–3.70 (1H, m, H-
5b), 4.35–4.48 (1H, m, H-2), 4.50–4.62 (1H, m, H-3) 5.0–5.20 (1H, m, O-CH2Ph),
6.50ꢀ7.0 (2H, br s, exchanges with D2O, COOH, OH), 7.18ꢀ7.42 (5H, m, ArꢀH);
13C NMR (75 MHz, CDCl3) d 32.1 (C-4), 44.4 (C-5), 63.8 (C-2), 67.3 (C-6), 70.8
(C-3), 127.5, 127.8, 128.3, 128.4, 136.1 (Ar), 155.4 (NCOO), 172.5 (COOH). The
NMR spectra of 11 showed additional signals due to presence of rotamers in a
ratio 3:1. In NMR data only high intensity signals are given. Anal. Calcd for
19. Pandey, S. K.; Kumar, P. Tetrahedron Lett. 2006, 47, 4167.
20. (a) Hughes, P. F.; Smith, S. H.; Olsen, J. T. J. Org. Chem. 1994, 59, 5799; (b) Masse,
C. E.; Morgan, A. J.; Panek, J. S. Org. Lett. 2000, 2, 2571.
C13H15NO5: C, 58.86; H, 5.70; N, 5.28. Found: C, 59.01; H, 5.88; N, 5.27. Data for
compound (ꢀ)-1: white solid, mp 221–228 °C (decomp.) [lit.13a 220ꢀ230 °C
21. Spectral and analytical data: Data for compound (7): white solid; mp 93–95 °C;
with decomp., lit.13e 222–228 °C, decomp.]; ½a 2D0
ꢁ
ꢀ99.2 (c 1.0, H2O) [lit.12c
[a]
D
Rf 0.40 (n-hexane/ethyl acetate = 7/3); ½a D20
ꢁ
ꢀ23.1 (c 1.3, CHCl3); IR (KBr) 1702,
ꢀ102.7 (c 1.0, H2O), lit.13a
[a
]
D
ꢀ101.0 (c 1.0, H2O)].
1628 cmꢀ1 1H NMR 300 MHz (CDCl3 + D2O) d 1.3 (3H, s, CH3), 1.50 (3H, s, CH3),
;