D
Synlett
X. Li et al.
Letter
molecule. Reactions like this are rare and quite important in
organic chemistry. Examples of this type of reaction include
the olefin-forming metathesis reaction, the Wittig reaction,
and the McMurry reaction. Because of the importance of
forming a carbon–carbon double bond in organic chemis-
try, this olefin-forming cascade reaction may be applied to
the synthesis of compounds similar to 7. Currently we are
testing the scope of this reaction by using “bromonitro”
compounds structurally similar to compound 12 and have
successfully synthesized several analogs using this olefin-
forming cascade reaction. The results will be reported in a
separate paper.
(12) Ono, N.; Miyake, H.; Tamura, R.; Hamamoto, I.; Kaji, A. Chem.
Lett. 1981, 1139.
(
13) (a) Chalk, A. J. J. Organomet. Chem. 1970, 21, 95. (b) Swamer, F.
W.; Hauser, C. R. J. Am. Chem. Soc. 1946, 68, 2647. (c) Lee, Y.-J.;
Closson, W. D. Tetrahedron Lett. 1974, 27, 381. (d) Natsume, M.;
Kumadaki, S. Tetrahedron Lett. 1973, 26, 2335. (e) Krief, A.;
Delmotte, C.; Dumont, W. Tetrahedron 1997, 53, 12147.
(f) Hayward, M. A.; Green, M. A.; Rosseinsky, M. J.; Sloan, J. J. Am.
Chem. Soc. 1999, 121, 8843.
(14) 2,2,2',2'-Tetramethyl[5,5']bi[1,3]dioxanylidene (7)
At r.t., under a N atmosphere, NaH (60% dispersion in mineral
2
oil, 1.05 g, 26 mmol) was added slowly to N,N-dimethylacet-
amide (DMA, 5 mL). A solution of 12 (1.22 g, 5.08 mmol) in
DMA (5 mL) was added dropwise to the stirred NaH suspension
at r.t. The temperature of the mixture was raised quickly to 80–
9
0 °C by placing it in a preheated oil bath. After 4 h, the reaction
mixture was allowed to cool to r.t., quenched in ice-cold water
10 mL), and extracted with anhydrous diethyl ether (3 x 15
Funding Information
(
This work was supported by funds from Southern Medical University
in Guangzhou China and Auburn University, Auburn, USA.
mL). The combined organic extracts were washed with cold
water (20 mL), dried with anhydrous Na SO , filtered, and the
)(
2
4
solvent evaporated under reduced pressure. The residue was
purified by silica gel flash chromatography (hexanes/EtOAc 4:1)
References and Notes
to yield a white solid (306 mg, 52.8%), mp 133.5–135 °C. 1
H
NMR (400 MHz, CD COCD ): δ = 4.22 (s, 4 H) 1.31 (s, 6 H) ppm.
(
(
(
1) Keough, T.; Ezra, F. S.; Russell, A. F.; Pryne, J. D. Org. Mass Spec-
3
3
13
C NMR (100 MHz, CD COCD ): δ = 125.7, 99.0, 58.2, 22.3 ppm.
trom. 1987, 22, 241.
2) Müller, S. N.; Batra, R.; Senn, M.; Giese, B.; Kisel, M.; Shadyro, O.
J. Am. Chem. Soc. 1997, 119, 2795.
3) Corson, B. B.; Benson, W. L. Org. Synth. Coll. Vol. 2; John Wiley &
Sons: London, 1943, 273.
3
3
(
15) 2,2,2',2'-Tetramethyl-[5,5']bi[[1,3]dioxanyl]-5,5'-diol (8)
In a 50 mL round-bottomed flask equipped with magnetic stir-
ring bar were stirred NaIO4 (160 mg, 0.75 mmol) and
CeCl ·7H O (19 mg, 0.051 mmol) in water (0.25 mL) and gently
3
2
heated until a bright yellow suspension was formed. After
cooling to 0 °C, ethyl acetate (0.63 mL) and acetonitrile (0.75
(
(
4) Plietker, B.; Niggemann, M. J. Org. Chem. 2005, 70, 2402.
5) Jie, Y.; Livant, P.; Li, H.; Yang, M.; Zhu, W.; Cammarata, V.;
Almond, P.; Sullens, T.; Qin, Y.; Bakker, E. J. Org. Chem. 2010, 75,
mL) were added, and the suspension was stirred for 2 min. RuCl3
(2.1 mg, 0.010 mmol) was added and the mixture was stirred
4
472.
6) Wang, X.; Li, X.; Xue, J.; Zhao, Y.; Zhang, Y. Tetrahedron Lett.
009, 50, 413.
for 2 min. A solution of olefin 7 (114 mg, 0.499 mmol) in ethyl
acetate (0.25 mL) was added in one portion. The mixture was
stirred until the starting material disappeared, monitored by
(
2
(
(
7) Ripoll, J.-L. Bull. Soc. Chim. Fr. 1974, 2567.
8) Crozet, M. P.; Archaimbault, G.; Vanelle, P.; Nouguier, R. Tetra-
hedron Lett. 1985, 26, 5133.
TLC (hexanes/EtOAc 4:1) every half hour. Na SO (250 mg) was
2
4
added followed by EtOAc (3 mL). The solid was filtered off. The
filtrate was washed with saturated Na SO (1.2 mL) solution.
(9) Hirayama, T.; Taki, M.; Nakamura, M.; Arata, T.; Yamamoto, Y.
2
3
The organic layer was dried with Na SO and concentrated with
Chem. Lett. 2006, 35, 834.
2
4
a rotary evaporator. The crude product was purified by chroma-
(
10) 2,2-Dimethyl-5-bromo-5-nitro-1,3-dioxane (12)
tography on silica gel (hexanes/EtOAc 2:1) to give a white solid,
To a solution of 2-bromo-2-nitro-1,3-propanediol (20.0 g, 0.101
mol) in 2,2-dimethoxypropane (80 mL) was added D-camphor-
1
(
83 mg, 63% yield), mp 187–190 °C. H NMR (400 MHz, CDCl ):
3
δ = 4.23 (d, 4 H, J = 12.0 Hz), 3.57 (d, 4 H, J = 12.0 Hz), 3.31 (s, 2
10-sulfonic acid (1.62 g, 8.09 mmol). The mixture was stirred
13
H), 1.46 (s, 6 H), 1.43 (s, 6 H). C NMR (100 MHz, CDCl ):
for 3 d at r.t. under a nitrogen atmosphere. The solvent was
evaporated with a rotary evaporator and residual solid was
3
δ = 98.7, 69.3, 64.5, 27.3, 20.0 ppm.
(
16) 2,3-Bis(hydroxymethyl)butane-1,2,3,4-tetraol (1)
At 0 °C, trifluoroacetic acid (0.10 mL, 1 mmol) was added to a
solution of 8 (71 mg, 0.27 mmol) in aqueous THF (2.5 mL,
purified by chromatography on silica gel (hexane/EtOAc 4:1) to
1
give 17.5 g of a colorless solid, 75.3% yield, mp: 79–81 °C
H
NMR (250 MHz, CDCl ): δ = 4.78 (d, 2 H, J = 13.5 Hz), 4.27 (d, 2
3
13
THF/H O 4:1). The mixture was stirred at r.t. for 3 h. The solu-
H, J = 13.5 Hz) 1.54 (s, 3 H) 1.37 (s, 3 H) ppm. C NMR (63 MHz,
2
tion was evaporated with a rotary evaporator affording a color-
CDCl ): δ = 99.6, 66.3, 28.1, 18.6 ppm.
3
less oil. After standing for several days, the colorless oil solidi-
(
11) Kornblum, N.; Boyd, S. D.; Pinnick, H. W.; Smith, R. G. J. Am.
1
fied, giving 1 (39 mg, 79% yield). H NMR (400 MHz, D Ο): δ =
Chem. Soc. 1971, 93, 4316.
2
13
3
.69 (s) ppm. C NMR (100 MHz, D O): δ = 76.9, 61.8 ppm.
2
©
Georg Thieme Verlag Stuttgart · New York — Synlett 2018, 29, A–D