Categories: Synthesis of O-Heterocycles >
Synthesis of dioxolanones
Recent Literature
Treatment of aldehydes with sulfur ylides, followed by a reaction with CO2
under mild conditions, produces cyclic carbonates in preparative yields. Sodium
iodide, which is formed in situ, promotes the reaction between the intermediate
epoxides with CO2 at ambient conditions, thus constituting a
versatile metal-free synthesis of organic cyclic carbonates from aldehydes.
R. D. Aher, B. S. Kumar, A. Sudalai, Synlett, 2014, 25,
97-101.
In cycloadditions of carbon dioxide into epoxides to afford cyclic carbonates, a
strained ion pair tris(alkylamino)cyclopropenium halide catalyst, in which the
halide is repelled, is a very electrophilic H-bond donor, allowing it to
activate the oxygen of the epoxide, while the more nucleophilic halide is better
able to attack the methylene carbon of the epoxide.
J. Xu, A. Xian, Z. Li, J. Liu, Z. Zhang, R. Yan, L. Gao, B. Liu, L. Zhao, K. Guo, J. Org. Chem., 2021, 86,
3422-3432.
A H8-binaphthyl-linked hemisquaramide catalyst accelerated the
synthesis of cyclic carbonates from epoxides and CO2 under mild and
solvent-free conditions. Kinetic resolution was also achieved at −20°C (s =
3.0).
K. Takaishi, T. Okuyama, S. Kadosaki, M. Uchiyama, T. Ema, Org. Lett., 2019, 21,
1397-1401.
Coupling reactions of epoxides with carbon dioxide that proceed at atmospheric
pressure at temperatures of less than 100°C are challenging.
Tetraarylphosphonium salts (TAPS) catalyze the formation of five-membered cyclic
carbonates by chemical fixation using 1 atm of carbon dioxide at 60°C.
Electron-donating groups enhanced the reactivity of the used TAPS.
Y. Toda, Y. Komiyama, H. Esaki, K. Fukushima, H. Suga, J. Org. Chem., 2019, 84,
15578-15589.
Complexes of phosphonium ylides and
metal halide salts efficiently catalyze the reaction of epoxides with carbon
dioxide under mild conditions to provide five-membered cyclic carbonates, including
disubstituted cyclic carbonates in good yields. Terminal epoxides could also be converted to
N-aryl oxazolidinones with isocyanates using a similar catalytic
system.
Y. Toda, K. Hashimoto, Y. Mori, H. Suga, J. Org. Chem., 2020, 85,
10980-10987.
In a simple and convenient method, NHC/ZnBr2 catalyzes the coupling
of CO2 with epoxides. This catalytic system exhibits excellent
activity and selectivity in the cycloaddition reactions of CO2 to
terminal epoxides. The reaction can even be carried out under partial CO2
pressure and gives carbonates in high yields.
X. Liu, C. Cao, Y. Li, P. Guan, L. Yang, Y. Shi, Synlett, 2012, 23,
1343-1348.
A series of charge-containing thiourea salts catalyze cycloadditions of
epoxides with CO2 under mild conditions to provide cyclic
five-membered ring organic carbonates of broad interest from a synthetic,
environmental, and green chemistry perspective.
Y. Fang, M. Tiffner, J. Schörgenhumer, R. Robiette, M. Waser, S. R. Kass, J. Org. Chem., 2018, 83,
9991-10000.
Acyclic guanidinium salts catalyze the formation of five-membered cyclic carbonates
in good yields through cycloaddition of CO2 to epoxides at nearly
ambient temperatures
and pressures. To achieve good catalytic activity of the guanidinium salt, it is essential to have
active hydrogens on the cation moiety as well as an iodide ion as the anion
moiety.
N. Aoyagi, Y. Furusho, T. Endo, Synthesis, 2020, 52,
150-158.
A reaction of diphenyl carbonate and various diols provides highly valuable cyclic carbonates
in the presence of
1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as organocatalyst. This practical, safe, and highly efficient carbonylation system
successfully
replaced highly toxic and unstable phosgene or its derivatives while maintaining
the desired high reactivity. Moreover, this new system can be used to synthesize
sterically demanding cyclic carbonates.
E. R. Baral, J. H. Lee, J. G. Kim, J. Org. Chem., 2018, 83,
11768-11776.
An efficient, versatile and practical gram-scale preparation of
oxazolidinone, imidazolidinone and dioxolanone is achieved.
N. Alouane, A. Boutier, C. Baron, E. Vrancken, P. Mangeney, Synthesis, 2006, 860-864.
Sequential treatment of a 1,2-disubstituted olefin with m-CPBA, Br3CCO2H,
and DBU results in the one-pot, stereospecific conversion of the olefin to the
corresponding disubstituted cyclic carbonate. When a solution of a secondary
allylic or homoallylic amine and Br3CCO2H is sequentially
treated with m-CPBA then DBU, the product of the reaction is a cyclic
carbamate.
S. G. Davies, A. M. Fletcher, W. Kurosawa, J. A. Lee, G. Poce, P. M. Roberts,
J. E. Thomson, D. M. Williamson, J. Org. Chem., 2010,
75, 7745-7756.
A series of tetrahaloindate(III)-based ionic liquids (ILs) have been
produced by microwave-assisted synthesis. These ionic liquids have been examined
as catalyst in the reaction of CO2 with various epoxides to give cyclic
carbonates. Tetrahaloindate(III)-based ILs are found to
exhibit high catalytic activities. The effects of a variety of parameters (temperature, pressure, molar ratio of propylene oxide to catalyst),
the mechanism, and the
significant role of H-bonding interactions in the coupling
reactions are discussed.
Y. J. Kim, R. S. Varma, J. Org. Chem., 2005, 70, 7882-7891.
The reaction of chiral 1-aminoalkylepoxides with CO2, generated from
acidic treatment of an aqueous solution of NaHCO3 at room temperature,
efficiently afforded enantiopure cyclic carbonates with total selectivity.
Carbonates were readily transformed into the corresponding diols by reaction
with LiAlH4 or by basic hydrolysis.
J. M. Concellón, V. del Solar, S. Carcía-Granda, M. R. Díaz, J. Org. Chem.,
2007,
72, 7567-7568.