Synthesis of oxazolidinones
Synthesis of oxazolidin-2-ones derivatives was carried out starting from urea and ethanolamine reagents using microwave irradiation in a chemical paste medium in which a catalytic amount of nitromethane absorbs the microwaves and generates hot spots.
G. Bratulescu, Synthesis, 2007, 3111-3112.
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.
A palladium-catalyzed N-arylation of 2-oxazolidinones with aryl bromides provides 3-aryl-2-oxazolidinones in good yields. The nature of aryl bromides, phosphine ligands, bases, and solvents strongly affects the reaction outcome.
S. Cacchi, G. Fabrizi, A. Goggiamani, G. Zappia, Org. Lett., 2001, 3, 2539-2541.
N,N'-Bis(pyridin-2-ylmethyl)oxalamide (BPMO) is an efficient ligand for the Cu-catalyzed N-arylation of oxazolidinones and amides with (hetero)aryl iodides at room temperature. The reactions offer excellent chemoselectivity between aryl iodides and aryl bromides and tolerate a wide range of functional groups.
S. Bhunia, S. De, D. Ma, Org. Lett., 2022, 24, 1253-1257.
Organoiodine(I/III) chemistry enables a metal-free, catalytic enantioselective intermolecular oxyamination of aryl- and alkyl-substituted alkenes with N-(fluorosulfonyl)carbamate as a bifunctional N,O-nucleophile with high enantioselectivity and electronically controlled regioselectivity. The oxyaminated products can be easily deprotected in one step to reveal free amino alcohols in high yields.
C. Wata, T. Hashimoto, J. Am. Chem. Soc., 2021, 143, 1745-1751.
The combination of visible-light photocatalysis and earth-abundant transition metal catalysis enables an intramolecular C(sp3)-H amination and oxygenation of unactivated carbamates to provide useful amino alcohol and diol derivatives from readily available tertiary alcohol derivatives.
Q. Guo, X. Ren, Z. Lu, Org. Lett., 2019, 21, 880-884.
A phosphazene base-catalyzed intramolecular hydroamidation of amide alkenes provides cyclic amides. The reaction using a catalytic amount of P4-base had a good functional group tolerance and a broad substrate scope and could also be used to synthesize lactams, cyclic ureas, and oxazolidinones.
J. Matsuoka, Y. Fujimoto, A. Miyawaki, Y. Yamamoto, Org. Lett., 2022, 24, 9447-9451.
An efficient sequential intramolecular cyclization of amino alcohol carbamates followed by Cu-catalyzed cross-coupling with aryl iodides under mild conditions gives N-aryl oxazolidinones in good yields. The reaction tolerated aryl iodides containing functionalities such as nitriles, ketones, ethers, and halogens. Heteroaryl iodides and substituted amino alcohol carbamates were can also be transformed.
W. Mahy, P. K. Plucinski, C. G. Frost, Org. Lett., 2014, 16, 5020-5021.
Carbonylimidazole derivatives are highly active acylation reagents for esterification and amidation in the presence of pyridinium salts as catalysts. These reactions are thought to involve both Brønsted acid and nucleophilic catalysis. This mode of activation has been applied to the synthesis of difficult to access oxazolidinones, as well as esters and amides.
S. T. Heller, T. Fu, R. Sarpong, Org. Lett., 2012, 14, 1970-1973.
Tetraarylphosphonium salts (TAPS) catalyze the [3 + 2] coupling reaction of isocyanates and epoxides to provide a range of oxazolidinones, including enantioenriched N-aryl-substituted oxazolidinones. These Brønsted acid/halide ion bifunctional catalysts accelerate epoxide ring opening with high regioselectivity.
Y. Toda, S. Gomyou, S. Tanaka, Y. Komiyama, A. Kikuchi, H. Suga, Org. Lett., 2017, 19, 5786-5789.
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.
Amidato lanthanide amides were applied in the cycloaddition reactions of aziridines with carbon dioxide (CO2) or carbon disulfide (CS2) under mild conditions to provide the corresponding oxazolidinones and thiazolidine-2-thiones in good yields with good functional group tolerance.
Y. Xie, C. Lu, B. Zhao, Q. Wang, Y. Yao, J. Org. Chem., 2019, 84, 1951-1958.
A functional-group-tolerant and scalable cobalt-catalyzed cyclization of alkenyl carbamates and alkenyl isoureas provides common five- and six-to-eight-membered cyclic carbamates and ureas via transition-metal hydrogen atom transfer and radical-polar crossover.
T. Nagai, N. Mimata, Y. Terada, C. Sebe, H. Shigehisa, Org. Lett., 2020, 22, 5522-5527.
Concerted proton-coupled electron transfer (PCET) mediated by an excited state iridium complex enables amide activation in the presence of a weak phosphate base to furnish a reactive amidyl radical that readily adds to pendant alkenes. The thiophenol cocatalyst furnishes the product and regenerate the active forms of the photocatalyst.
D. C. Miller, G. J. Choi, H. S. Orbe, R. R. Knowles, J. Am. Chem. Soc., 2015, 137, 13492-13495.
An electrochemically mediated carboxylative cyclization of allylic amines with CO2 provdies 2-oxazolidinones. As opposed to previous addition reactions, the unsaturated double bonds are preserved. Furthermore, this method can also be applied to the synthesis of six-membered heterocycles (1,3-oxazinan-2-ones).
Y.-Z. Pan, Q. Xia, J.-X. Zhu, Y.-C. Wang, Y. Liang, H. Wang, H.-T. Tang, Y.-M. Pan, Org. Lett., 2022, 24, 8239-8243.
A mild Pd-catalyzed ring-opening cyclization reaction of 2-vinylaziridines with an ambient atmosphere of carbon dioxide gives 5-vinyloxazolidinones in high yield as well as regio- and stereoselectivity.
F. Fontana, C. C. Chen, V. K. Aggarwal, Org. Lett., 2011, 13, 3454-3457.
An oxidative cleavage of alkyl C-Pd bond by H2O2 enables a palladium-catalyzed intramolecular aminohydroxylation to give various heterocycles with good yields and excellent diastereoselectivities. Facile transformation of these products provided a powerful tool toward the synthesis of 2-amino-1,3-diols and 3-ol amino acids. Preliminary mechanistic studies revealed that a SN2 type attack of water at a high-valent Pd center is involved.
H. Zhu, P. Chen, G. Liu, J. Am. Chem. Soc., 2014, 136, 1766-1769.
3-Aryl- and 3-heteroaryl-5-(iodomethyl)oxazolidin-2-ones can readily be prepared by the iodocyclocarbamation reaction of N-allylated N-aryl or N-heteroaryl carbamates. These structures are useful intermediates for the rapid preparation of potential lead compounds with biological activity.
A. C. Bell, A. B. Boomsma, N. E. Flikweert, R. M. Hohlman, S. Zhang, R. L. Blankespoor, S. M. Biros, R. J. Staples, S. J. Brickner, M. R. Barbachyn, J. Org. Chem., 2020, 85, 6323-6337.
The combination of a binuclear tridentate copper(I) complex and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) provided a catalytic system for the synthesis of a wide range of oxazolidinones from various propargylic amines and CO2 under mild reaction conditions.
F. Chen, S. Tao, Q.-Q. Deng, D. Wei, N. Liu, B. Dai, J. Org. Chem., 2020, 85, 15197-15212.
A silver-catalyzed carbon dioxide incorporation reaction into various propargylic amines provides oxazolidinone derivatives under mild reaction conditions in excellent yields. The geometry of the C-C double bond in the product was confirmed by X-ray analysis.
S. Yoshida, K. Fukui, S. Kikuchi, T. Yamada, Chem. Lett., 2009, 786-787.
The use of Pd(OAc)2 and n-Bu4NOAc as catalysts enables an efficient and simple synthesis of oxazolidinones, oxazolidinthiones, imidazolidinthiones, and imidazolidinones from the corresponding propargylic starting materials in DCE at room temperature.
S. K. Alamsetti, A. K. Å. Persson, J.-E. Bäckvall, Org. Lett., 2014, 16, 1434-1437.
A mild and efficient gold(I)-catalyzed rearrangement of propargylic tert-butylcarbamates allows the synthesis of various 5-methylene-1,3-oxazolidin-2-ones, which would be less conveniently obtained using other methods.
A. Buzas, F. Gagosz, Synlett, 2006, 2727-2730.
Various N-Boc-protected alkynylamines are converted into the corresponding alkylidene 2-oxazolidinones or 2-oxazinones under very mild reaction conditions in the presence of a cationic Au(I) complex in high yield regardless of the substitution at nitrogen and alkyne terminus.
R. Robles-Machin, J. Adrio, J. C. Carretero, J. Org. Chem., 2006, 71, 4951-4955.
The use of a combination of silver acetate and N,N-dimethylaminopyridine enables a highly Z-selective syntheses of oxazolidin-2-ones from propargylic alcohols containing internal alkynes and phenyl isocyanate. The silver catalyst effectively activates the C≡C triple bond by acting as a π-Lewis acid to produce the corresponding oxazolidinones with high Z-selectivities.
K. Sekine, T. Mawatari, T. Yamada, Synlett, 2015, 26, 2447-2450.
A nickel-catalyzed cycloaddition of aziridines with isocyanates proceeded smoothly to give iminooxazolidine derivatives in good yields. A longer reaction time allowed the isomerization of the iminooxazolidine to the corresponding imidazolidinone derivatives.
T. Munegumi, I. Azumaya, T. Kato, H. Masu, S. Saito, Org. Lett., 2006, 8, 379-382.