2
124
O. V. Turova et al. / Tetrahedron: Asymmetry 20 (2009) 2121–2124
2
D
0
CN). 1H NMR (d, ppm,
0
CDCl
1
2
.186, CH
2
Cl
): 4.52–4.44 (m, 1H, PrCH), 3.67 (s, 3H, OMe), 3.03–2.93 (m,
CO), 2.80 (dd, J = 17.8 Hz, J = 8.5 Hz, 1H, CH CO),
.67 (dd, J = 17.8 Hz, J = 9.7 Hz, 1H, CH CO), 1.69-1.59 (m, 2H,
CH CH), 1.50-1.26 (m, 2H, MeCH CH CH), 0.87 (t,
J = 7.4 Hz, 3H, MeCH CH ): 174.26
CH). 13C NMR (d, ppm, CDCl
CO) 171.45 (COOMe), 81.47 (PrCHO), 52.39 (COOMe), 45.31
CHCOOMe), 37.10 (MeCH CH CH), 31.85 (CH CO), 18.31
MeCH CH CH), 13.42 (MeCH CH CH). MS, m/z: 186 (9), 158 (50),
55 (53), 144 (88), 143 (97), 130 (25), 127 (28), 126 (45), 115
100), 101 (35), 99 (28), 83 (67), 74 (27), 71 (85), 69 (54), 59
50), 55 (86), 43 (11). Anal. Calcd for C : C, 58.05; H, 7.58.
2
), ½
a
ꢂ
¼ þ39:4 (c 0.164, CH
3
nent), 1.1; (2R,3R), (major), 7.7; (2S,3S), (minor), 8.0;
2
0
1
3
½
a
ꢂ
D
¼ þ38:0 (c 0.108, CH
2
Cl
J = 8.8 Hz, J = 6.3 Hz, 1H, i-PrCH), 3.76 (s, 3H, OMe), 3.47–3.37 (m,
1H, CHCH CO), 2.82 (dd, J = 17.4 Hz, J = 3.6 Hz, 1H, CH CO),
2.70 (dd, J = 17.4 Hz, J = 7.9 Hz, 1H, CH CO), 1.94-1.75 (m, 1H,
Me CHCH), 1.09 (d, J = 6.5 Hz, 3H, Me(Me)CHCH), 1.00 (d,
J = 6.5 Hz, 3H, Me(Me)CHCH). C NMR (d, ppm, CDCl
(CH CO), 170.75 (COOMe), 85.78 (i-PrCHO), 51.74 (COOMe), 43.40
(CHCOOMe), 32.97 (CH CO), 29.85 (MeCH(Me)CH), 18.91 (MeCH(-
2 3
). H NMR (d, ppm, CDCl ): 4.2 (dd,
H, CHCH
2
a b
H
a
H
b
2
a b
H
MeCH
2
2
2
2
a b
H
2
2
3
2
1
3
(
(
(
CH
2
3
): 174.36
2
2
2
2
2
2
2
2
2
1
(
(
Me)CH), 17.96 (MeCH(Me)CH). MS, m/z: 186 (27), 168 (24), 155
(50), 144 (69), 143 (69), 140 (31), 127 (24), 126 (45), 115 (80),
101 (12), 99 (33), 83 (100), 72 (38), 71 (41), 69 (79), 55(63), 43
9 14 4
H O
Found: C, 57.84; H, 7.45.
9 14 4
(7). Anal. Calcd for C H O : C, 58.05; H, 7.58. Found: C, 57.79; H,
7
.39.
4
.3.6. Methyl (2R,3R)-2-propyl-5-oxo-tetrahydrofuran-3-
carboxylate 11c
= 0.38. IR, cm 1: 1784, 1740.
ꢀ
References
Yield: 90.9 mg, solid, mp 42 °C, R
f
GLC [retention time (t ), min, He, 145 °C]: CH (non-sorbable com-
ponent), 1.1; (2R,3R), (major), 7.7; (2S,3S), (minor), 8.4;
R
4
1
.
(a) Crawforth, J. M.; Fawcett, J.; Rawlings, B. J. J. Chem. Soc., Perkin Trans. 1 1998,
721–1725; (b) Mori, K.; Chiba, N. Liebigs Ann. Chem. 1989, 957–962; (c) Mori,
K.; Yamane, K. Tetrahedron 1982, 38, 2919–2921; (d) Mori, K. Tetrahedron 1983,
1
2
D
0
20
D
CN). 1
½
a
ꢂ
¼ þ94:0 (c 0.328, CH
2
Cl
2
), ½
a
ꢂ
¼ þ93:2 (c 0.16, CH
3
H
3
2
9, 3107–3109; (e) Bandichhor, R.; Nosse, B.; Reiser, O. Top. Curr. Chem. 2005,
43, 43–72.
NMR (d, ppm, CDCl
.40–3.30 (td, J = 15.6 Hz, J = 5.1 Hz, 1H, CHCH
J = 17.5 Hz, J = 5.0 Hz, 1H, CH CO), 2.58 (dd, J = 17.5 Hz,
J = 8.6 Hz, 1H, CH CO), 1.65-1.23 (m, 4H, MeCH CH CH), 0.84
3
): 4.58–4.49 (m, 1H, PrCH), 3.63 (s, 3H, OMe),
3
2
CO), 2.73 (dd,
2
.
Horhant, D.; Le Lamer, A.-C.; Boustie, J.; Uriac, P.; Gouault, N. Tetrahedron Lett.
2007, 48, 6031–6033 and references cited therein.
a
H
b
H
b
2
2
3. (a) Hajra, S.; Karmakar, A.; Giri, A. K.; Hazra, S. Tetrahedron Lett. 2008, 49, 3625–
3627; (b) Hon, Y.-S.; Hsieh, C.-H.; Liu, Y.-W. Tetrahedron 2005, 61, 2713–2723;
a
CH). 1 C NMR (d, ppm, CDCl
): 174.86
CO) 170.89 (COOMe), 80.04 (PrCHO), 51.93 (COOMe), 44.00
CHCOOMe), 33.14 (MeCH CH CH), 31.74 (CH CO), 18.91
MeCH CH CH), 13.42 (MeCH CH CH). MS, m/z: 186 (8), 168 (15),
55 (61), 154 (49), 144 (41), 143 (89), 140 (45), 130 (9), 127
3
(
(
(
(
t, J = 7.0 Hz, 3H, MeCH
2
CH
2
3
(
c) Barros, M. T.; Maycock, C. D.; Ventura, M. R. Org. Lett. 2003, 5, 4097–4099; (d)
CH
2
Sibi, M. P.; Liu, P.; Ji, J.; Hajra, S.; Chen, J.-X. J. Org. Chem. 2002, 67, 1738–1745; (e)
Kongsaeree, P.; Meepowpan, P.; Thebtaranonth, Y. Tetrahedron: Asymmetry 2001,
2
2
2
1
2, 1913–1922; (f) Bella, M.; Margarita, R.; Orlando, C.; Orsini, M.; Parlanti, L.;
2
2
2
2
Piancatelli, G. Tetrahedron Lett. 2000, 41, 561–565; (g) Jacobi, P. A.; Herradura, P.
Tetrahedron Lett. 1996, 37, 8297–8300; (h) Zhaoguo, Z.; Lu, X. Tetrahedron:
Asymmetry 1996, 7, 1923–1928; (i) Zhu, G.; Lu, X. Tetrahedron: Asymmetry 1995,
1
(
(
32), 126 (71), 115 (88), 101 (17), 99 (16), 83 (77), 74 (15), 72
22), 71 (65), 69 (29), 59 (49), 55 (100), 43 (12). Anal. Calcd for
6
5
, 885–892; (j) Takahata, H.; Uchida, Y.; Momose, T. J. Org. Chem. 1995, 60, 5628–
633; (k) Mawson, S. D.; Weavers, R. T. Tetrahedron 1995, 51, 11257–11270; (l)
C H
9 14
O
4
: C, 58.05; H, 7.58. Found: C, 57.79; H, 7.40.
Banks, M. R.; Dawson, I. M.; Gosney, I.; Hodgson, P. K. G.; Thorburn, P.
Tetrahedron Lett. 1995, 36, 3567–3570; (m) Mulzer, J.; Salimi, N.; Hartl, H.
Tetrahedron: Asymmetry 1993, 4, 457–471; (n) Murta, M. M. J. Org. Chem. 1993,
4
.3.7. Methyl (2R,3S)-2-isopropyl-5-oxo-tetrahydrofuran-3-
5
8, 7537–7541.
carboxylate 10d
4
.
.
Drioli, S.; Felluga, F.; Forzato, C.; Nitti, P.; Pitacco, G.; Valentin, E. J. Org. Chem.
1998, 63, 2385–2388.
ꢀ
Yield: 100.5 mg, R
f
= 0.50. IR, cm 1: 1784, 1740. GLC [retention
5
(a) Blanc, D.; Madec, J.; Popowyck, P.; Ayad, T.; Phansavath, P.; Ratovelomanana-
Vidal, V.; Genêt, J.-P. Adv. Synth. Catal. 2007, 349, 943–950; (b) Starodubtseva, E.
V.; Turova, O. V.; Vinogradov, M. G.; Gorshkova, L. S.; Ferapontov, V. A.;
Struchkova, M. I. Tetrahedron 2008, 64, 11713–11717; (c) Starodubtseva, E. V.;
Turova, O. V.; Vinogradov, M. G.; Gorshkova, L. S.; Ferapontov, V. A. Russ. Chem.
Bull. 2005, 2374–2378 [Engl. Transl. from Izvestiya Academii Nauk. Seriya
Khimicheskaya 2005, 2301–2304]; (d) Braukmüller, S.; Brückner, R. Eur. J. Org.
Chem. 2006, 2110–2118; (e) Martin, T.; Rodriguez, C. M.; Martin, V. S. J. Org.
Chem. 1996, 61, 6450–6453.
(a) Comini, A.; Forzato, C.; Nitti, P.; Pitacco, G.; Valentin, E. Tetrahedron:
Asymmetry 2004, 15, 617–625; (b) Berti, F.; Felluga, F.; Forzato, C.; Furlan, G.;
Nitti, P.; Pitacco, G.; Valentin, E. Tetrahedron: Asymmetry 2006, 17, 2344–2353;
(c) Forzato, C.; Furlan, G.; Nitti, P.; Pitacco, G.; Marchesan, D.; Coriani, S.;
Valentin, E. Tetrahedron: Asymmetry 2005, 16, 3011–3023; (d) Forzato, C.; Furlan,
G.; Nitti, P.; Pitacco, G.; Valentin, E.; Zangrando, E.; Buzzini, P.; Goretti, M.;
Turchetti, B. Tetrahedron: Asymmetry 2008, 19, 2026–2036; (e) Berti, F.; Forzato,
C.; Furlan, G.; Nitti, P.; Pitacco, G.; Valentin, E.; Zangrando, E. Tetrahedron:
Asymmetry 2009, 20, 313–321; (f) Kim, H.-C.; Park, O.-S. Tetrahedron: Asymmetry
time (t
2S,3R), (minor), 5.4; (2R,3S), (major), 5.8; ½
R
), min, He, 145 °C]: CH (non-sorbable component oil,), 1.1;
4
20
(
a
ꢂ
¼ þ23:9 (c 0.304,
D
2
D
0
CN). 1H NMR (d, ppm, CDCl
CH
.39–4.33 (m, 1H, i-PrCH), 3.69 (s, 3H, OMe), 3.12–3.03 (m, 1H,
CHCH CO), 2.82 (dd, J = 17.9 Hz, J = 7.9 Hz, 1H, CH CO), 2.70
dd, J = 17.9 Hz, J = 9.9 Hz, 1H, CH CO), 1.94-1.80 (m, 1H,
2
Cl
2
), ½a
ꢂ
¼ þ24:9 (c 0.318, CH
3
3
):
4
2
a b
H
(
a b
H
13
Me
CDCl
(
1
2
CHCH), 0.93 (t, J = 6.4 Hz, 6H, Me
): 174.31 (CH CO) 172.13 (COOMe), 86.33 (i-PrCHO), 52.47
COOMe), 42.61 (CHCOOMe), 32.34 (CH CO), 32.32 (MeCH(Me)CH),
7.55 (MeCH(Me)CH), 17.02 (MeCH(Me)CH). MS, m/z: 186 (6), 158
2
CHCH). C NMR (d, ppm,
6
.
3
2
2
(
(
42), 155 (50), 144 (83), 143 (100), 127 (31), 126 (60), 115 (97), 101
38), 99 (16), 83 (84), 74 (21), 72 (27), 71 (70), 69 (38), 59 (54),
5
9 14 4
5(70), 43 (10). Anal. Calcd for C H O : C, 58.05; H, 7.58. Found:
C, 57.79; H, 7.39.
2008, 19, 896–899; (g) Drutu, I.; Krygowski, E. S.; Wood, J. L. J. Org. Chem. 2001,
6
6, 7025–7029; (h) Mohr, P.; Rösslein, L.; Tamm, C. Tetrahedron Lett. 1989, 30,
4
.3.8. Methyl (2R,3R)-2-isopropyl-5-oxo-tetrahydrofuran-3-
2513–2516; (i) Hoffmann, N. Tetrahedron: Asymmetry 1994, 5, 879–886.
Vinogradov, M. G.; Starodubtseva, E. V.; Turova, O. V. Russ. Chem. Rev. 2008, 77,
725–737 [Engl. Transl. from Uspekhi Khimii 2008, 77, 773–786].
7.
carboxylate 11d
= 0.66. IR, cmꢀ1: 1784, 1740. GLC
R 4
retention time (t ), min, He, 145 °C]: CH (non-sorbable compo-
Yield: 7 mg, solid, mp 92 °C, R
f
[