J. C. Jung et al. / Tetrahedron Letters 52 (2011) 4662–4664
4663
Table 1
Table 2
b-(1,3-Dioxolanylation) of electron-deficient olefins
b-(2-Methyl-1,3-dioxolanylation) of electron-deficient olefins
O
O
O
O
O
Me
Me
R2
R1
R2
X
O
X
X
R1
R2
X
(n-Bu4N)2S2O8
O
O
+
(n-Bu4N)2S2O8
+
25 oC, Ar
R1
R1
ClCH2CH2Cl,
70 oC, Ar
R2
1
2
3
1
2
5
Yielda
(%)
Run Olefin (1)
Rxn time
(h)
Product (3)
Yielda
(%)
Run Olefin (1)
Time
(min)
Product (5)
O
O
O
MeO2C
CO2Me
CO2Me
MeO2C
CO2Me
CO2Me
Me
CO2Me
CO2Me
O
CO2Me
CO2Me
1
1.5
98
1
20
96
70
MeO2C
MeO2C
O
O
O
Me
O
MeO2C
O
2
3
MeO2C
Me
1.5
15
98
98
2
MeO2C
Me
30
MeO2C
CO2Me
CO2Me
O
O
Me
CO2Me
O
CO2Me
3
4
5
150
30
99
60
66
Me
O
Me
O
CO2Et
Me
O
CO2Et
O
O
4
5
20
18
71
97
O
O
O
O
O
O
Me
O
90
O
O
O
O
O
O
O
O
6
54
73
O
O
Me
Me
6
7
90
30
80
48
O
O
O
SO2Ph
7
8
44
3
90
99
O
SO2Ph
O
O
O
SO2Ph
SO2Ph
a
Isolated yield after flash column chromatography.
O
a
Isolated yield after flash column chromatography.
4. (a) Campari, G.; Fagnoni, M.; Mella, M.; Albini, A. Tetrahedron: Asymmetry 2000,
11, 1891; (b) Manfrotto, C.; Mella, M.; Freccero, M.; Fagnoni, M.; Albini, A. J. Org.
Chem. 1999, 64, 5024; (c) Mase, N.; Watanabe, Y.; Toru, T. Bull. Chem. Soc. Jpn.
1998, 71, 2957; (d) Inomata, K.; Suhara, H.; Kinoshita, H. Chem. Lett. 1988, 813;
(e) Matsukawa, M.; Inanaga, J.; Yamaguchi, M. Tetrahedron Lett. 1987, 28, 5877;
(f) Giordano, C.; Minisci, F.; Vismara, F.; Levi, S. J. Org. Chem. 1986, 51, 536; (g)
Watanabe, Y.; Tsuji, Y.; Takeuchi, R. Bull. Chem. Soc. Jpn. 1983, 56, 1428.
5. (a) Hwang, J. P.; Yang, S. G.; Kim, Y. H. J. Chem. Soc., Chem. Commun. 1997, 1335;
(b) Kim, Y. H.; Hwang, J. P.; Yang, S. G. Tetrahedron Lett. 1997, 38, 3009; (c) Choi,
H. C.; Cho, K. I.; Kim, Y. H. Synlett 1995, 207; (d) Jung, J. C.; Choi, H. C.; Kim, Y. H.
Tetrahedron Lett. 1993, 34, 3581.
precursors for the synthesis of cyclopentanoids and furanoids,10
heteroaromatics,11 and also bioactive natural products such as
cis-jasmone, rethrolones, and prostaglandin B2.12
In summary, we have shown that various types of electron-defi-
cient olefins reacted readily with 1,3-dioxolane or 2-methyl-1,3-
dioxlane in the presence of TBAP to provide the corresponding
1,3-dioxolanylated or 2-methyl-1,3-dioxolanylated products,
formylation or acetylation equivalents, in a complete regioselective
way in good to excellent yields. These novel 1,4-addition reactions
are practically useful for the synthesis of formyl and acetyl func-
tional groups which could play a commanding role in the construc-
tion of complex molecular architecture. Further studies to
determine the scope and the reaction mechanism are actively
going on, and the results will be reported in due course.
6. Typical experimental procedure: Dimethyl maleate (72.1 mg, 0.50 mmol) and
TBAP (677.0 mg, 1.0 mmol) were added to dry 1,3-dioxolane (5 mL), and the
reaction mixture was stirred at 25 °C for 1.5 h under Ar. The reaction mixture
was concentrated to give a viscous oil which was diluted with H2O (5 mL), then
extracted with CH2Cl2 (10 mL Â 3). The combined organic layers were dried
over anhyd MgSO4, filtered and concentrated to give an oily residue which was
flash chromatographed (SiO2, Et2O/hexane = 1:3) to afford pure dimethyl 2-
(1,3-dioxolan-2-yl)butanedioate (106.9 mg, 98%). IR (NaCl, neat) 1737, 1187,
; d 2.63 (dd, 1H, –CHCHH–,
1023, 946 cmÀ1 1H NMR (CDCl3, 400 MHz)
J1 = 17.1 Hz, J2 = 4.9 Hz), 2.80 (dd, 1H, –CHCHH–, J1 = 17.1 Hz, J2 = 9.3 Hz), 3.25
(br q, 1H, –CHCH2–), 3.68 (s, 3H, –OCH3), 3.75 (s, 3H, –OCH3), 3.85–4.01 (m, 4H,
–CH2CH2–), 5.19 (d, 1H, –CHCH–, J = 4.4 Hz); 13C NMR (CDCl3, 100 MHz) d
29.90, 45.54, 51.74, 52.16, 65.24, 102.60, 102.62, 171.28, 172.25, MS (EI) m/z
(rel. intensity %) 99 (11), 73 (100), 59 (27), 55 (38), 45 (48).
Acknowledgments
This work was supported by Korean Science & Engineering
Foundation. Lee, K. gratefully acknowledges the financial support
from the Program of Regional Innovation Center at Woosuk Uni-
versity which was conducted by the Ministry of Knowledge Econ-
omy of the Korean Government.
7. Mosca, R.; Fagnoni, M.; Mella, M.; Albini, A. Tetrahedron 2001, 57, 10319.
8. Typical experimental procedure:
A mixture of methyl crotonate (50.1 mg,
0.50 mmol), TBAP (677.0 mg, 1.0 mmol) and 2-methyl-1,3-dioxolane
(881.1 mg, 10.0 mmol) in anhyd dichloroethane (2 mL) was heated at 70 °C
for 2.5 h under Ar. The reaction mixture was concentrated to give a viscous oil
which was diluted with saturated aqueous NaHCO3 (1 mL) and distilled H2O
(10 mL). The product was extracted with Et2O (10 mL Â 3), and the combined
organic layers were dried over anhyd MgSO4, filtered and concentrated. The
oily residue was purified by flash chromatography on SiO2 (Et2O/hexane = 1:3)
to afford methyl 3-(2-methyl-1,3-dioxolan-2-yl)butanoate (93.0 mg, 99 %). IR
References and notes
1. (a) Curran, D. P. Synthesis 1988, 417, 489; (b) Giese, B. Angew. Chem., Int. Ed.
Engl. 1985, 24, 553.
(NaCl, neat) 1733, 1195, 1160, 1051, 951 cmÀ1 1H NMR (CDCl3, 400 MHz) d
;
2. (a) Bottegi, C.; Soccolini, F. Synthesis 1985, 592; (b) El-Bouz, M.; Wartsk, L.
Tetrahedron Lett. 1980, 21, 2897.
3. Ji, H.-B. Eur. J. Org. Chem. 2003, 3659. Other important references cited therein.
102 (d, 3H, CH3CH–, J = 6.8 Hz), 1.27 (s, 3H, CH3C–), 2.09 (dd, 1H, –CHCHH–,
J1 = 15.1 Hz, J2 = 8.3 Hz), 2.27–2.37 (m, 1H, –CHCH2–), 2.57 (dd, 1H, –CHCHH–,
J1 = 15.1 Hz, J2 = 5.4 Hz), 3.67 (s, 3H, –CO2CH3), 3.87–4.01 (m, 4H, –CH2CH2–);