Synthesis of thiazoles
Treatment of N,N-diformylaminomethyl aryl ketones with phosphorus pentasulfide and triethylamine in chloroform gives 5-arylthiazoles in good yield. The 5-aryl-1,3-thiazole core has been successfully functionalised at the 2-position to yield, over two steps, a large array of 5-aryl-2-arylsulfonyl-1,3-thiazoles.
P. W. Sheldrake, M. Matteucci, E. McDonald, Synlett, 2006, 460-462.
A copper-catalyzed [3+1+1]-type condensation of oximes, anhydrides and potassiumthiocyanate (KSCN) provides thiazoles in very good yields under mild reaction conditions. The transformation has good functional group tolerance.
X. Tang, J. Yang, Z. Zhu, M. Zheng, W. Wu, H. Jiang, J. Org. Chem., 2016, 81, 11461-11466.
Practical Cu-catalyzed oxidative, multiple Csp3-H bond cleavage processes achieve a synthesis of thiazoles from simple aldehydes, amines, and element sulfur in the presence of molecular oxygen as a green oxidant.
X. Wang, X. Qiu, J. Wei, J. Liu, S. Song, W. Wang, N. Jiao, Org. Lett., 2018, 20, 2632-2636.
Ligand-free Pd(OAc)2 catalyzes very efficiently the direct arylation of thiazole derivatives under very low catalyst concentration. Reactions with activated aryl bromides can be performed employing as little as 0.1-0.001 mol % catalyst, whereas some strongly deactivated or highly congested aryl bromides only give disappointing results.
J. Roger, F. Pogan, H. Doucet, J. Org. Chem., 2009, 74, 1179-1186.
Conditions for the palladium-catalyzed direct arylation of a wide range of heterocycles with aryl bromides employ a stoichiometric ratio of both coupling partners, as well as a substoichiometric quantity of pivalic acid, which results in significantly faster reactions. An evaluation of the influence of the nature of the aryl halide has also been carried out.
B. Liégault, D. Lapointe, L. Caron, A. Vlassova, K. Fagnou, J. Org. Chem., 2009, 74, 1826-1834.
Base-induced cyclization of active methylene isocyanides such as tosylmethyl isocyanide, ethyl isocyanoacetate, and arylmethyl isocyanides with methyl arene- and hetarenecarbodithioates enables an efficient synthesis of 4,5-disubstituted thiazoles. This synthesis is simple, rapid, and often avoids purification steps.
G. S. Lingaraju, T. R. Swaroop, A. C. Vinayaka, K. S. S. Kumar, M. P. Sadashiva, K. S. Ragappa, Synthesis, 2012, 44, 1373-1379.
1-sulfonyl-1,2,3-triazoles react with thionoesters in the presence of a rhodium(II) catalyst providing 3-sulfonyl-4-thiazolines, which subsequently aromatize into the corresponding 2,5-disubstituted thiazoles by elimination of the sulfonyl group.
T. Miura, Y. Funakoshi, Y. Fujimoto, J. Nakahashi, M. Murakami, Org. Lett., 2015, 17, 2454-2457.
Hantzsch condensation of 2-bromoacetophenones with thiourea or selenourea enables a simple, fast, and eco-friendly solvent-free synthesis of 2-aminothiazoles and 2-amino-1,3-selenazoles without the use of a catalyst. Reactions proceed to completion in a few seconds and products are obtained in good yields after easy workup.
V. Facchinetti, M. M. Avellar, A. C. S. Nery, C. R. B. Gomes, T. R. A. Vasconcelos, M. V. N. de Souza, Synthesis, 2016, 48, 437-440.
Palladium(II) acetate catalyzes a highly selective construction of 4-substituted 2-aminothiazoles from vinyl azides and potassium thiocyanate, whereas iron(III) bromide promotes the formation of 4-substituted 5-thiocyano-2-aminothiazoles. Use of readily available starting materials, high selectivity, as well as mild reaction conditions make these practical methods particularly attractive.
B. Chen, S. Guo, X. Guo, G. Zhang, Y. Yu, Org. Lett., 2015, 17, 4698-4701.
A copper-catalyzed coupling of oxime acetates with isothiocyanates provides various 4-substituted and 4,5-disubstituted 2-aminothiazoles under mild reaction conditions via copper-catalyzed N-O bond cleavage, activation of vinyl sp2 C-H bonds, and C-S/C-N bond formations. The oxime acetates serve not only as substrate but also as single oxidant.
X. Tang, Z. Zhu, C. Qi, W. Wu, H. Jiang, Org. Lett., 2016, 18, 180-183.
A one-pot three-component reaction of α-nitro epoxides, potassium thiocyanate, and primary amines provides polysubstituted 2-aminothiazoles in a smooth, highly efficient, and eco-friendly manner with good yields.
Y. Zhu, W. Chen, D. Zhao, G. Zhang, Y. Yu, Synthesis, 2019, 51, 2023-2029.
The use of tribromoisocyanuric acid enables a simple and efficient one-pot protocol for the synthesis of 2-aminothiazoles from readily available β-keto esters via α-monohalogenation in aqueous medium and a subsequent reaction with thiourea and DABCO. Extension of the reaction to thioacetamide and o-phenylenediamine led to 2-methylthiazole and quinoxalines, respectively.
V. S. C. de Andrade, M. C. S. de Mattos, Synthesis, 2018, 50, 4867-4874.
A domino alkylation-cyclization reaction of propargyl bromides with thioureas and thiopyrimidinones allows the synthesis of 2-aminothiazoles and 5H-thiazolo[3,2-a]pyrimidin-5-ones, respectively. Domino reactions were performed under microwave irradiation leading to desired compounds in a few minutes and high yields.
D. Castagnolo, M. Pagano, M. Bernardini, M. Botta, Synlett, 2009, 2093-2096.
A small library of compounds with oxazole and thiazole scaffolds and structural diversity in both positions 2 and 5 has been synthesized. Double acylation of a protected glycine affords intermediate α-amido-β-ketoesters, which in turn can be dehydrated to afford 1,3-oxazoles or reacted with Lawesson’s reagent to furnish 1,3-thiazoles.
J. F. Sanz-Cervera, R. Blasco, J. Piera, M. Cynamon, I. Ibáñez, M. Murguía, S. Fustero, J. Org. Chem., 2009, 74, 8988-8996.
2-Amino-4-alkyl- and 2-amino-4-arylthiazole-5-carboxylates and their selenazole analogues were synthesized by α-halogenation of β-keto esters with N-bromosuccinimide, followed by cyclization with thiourea or selenourea, respectively, in the presence of β-cyclodextrin in water at 50°C.
M. Narender, M. S. Reddy, V. P. Kumar, B. Srinivas, R. Sridhar, Y. V. D. Nageswar, K. R. Rao, Synthesis, 2007, 3469-3472.
Thiazoles were obtained in good yields by the reaction of 1H-1-(1′-alkynyl)-5-methyl-1,2,3-benziodoxathiole 3,3-dioxides with thioamides. The co-product, potassium 2-iodo-5-methylbenzenesulfonate, was recovered quantitatively by simple filtration of the reaction mixture, and was regenerated to 1H-1-(1′-alkynyl)-5-methyl-1,2,3-benziodoxathiole 3,3-dioxides to be reused.
Y. Ishiwata, H. Togo, Synlett, 2008, 2637-2641.
Endothiopeptides can easily be obtained via Ugi reaction using thio acids as acid components. If isonitriles with an acetal group are applied, the endothiopeptides can directly be converted into thiazoles using TMSCl-NaI under microwave irradiation.
U. Kazmaier, S. Ackermann, Org. Biomol. Chem., 2005, 3, 3184-3187.
Thionation of amides, 1,4-diketones, N-(2-oxoalkyl)amides, and N,N'-acylhydrazines with the use of a fluorous Lawesson's reagent leads to thioamides, thiophenes, 1,3-thiazoles, and 1,3,4-thiadiazoles in high yields. The isolation of the final products is achieved in most cases by a simple filtration.
Z. Kaleta, B. T Makowski, T. Soos, R. Dembinski, Org. Lett., 2006, 8, 1625-1628.
A new method for a direct, copper-catalyzed arylation of heterocycle C-H bonds by aryl iodides allows the conversion of electron-rich five-membered heterocycles and electron-poor pyridine oxides. The best results are obtained by using a combination of lithium tert-butoxide as base and copper iodide as catalyst.
H.-Q. Do, O. Daugulis, J. Am. Chem. Soc., 2007, 129, 12404-12405.
A Regel-type transition-metal-free direct C-2 aroylation of (benzo)oxazoles, (benzo)thiazoles and 1,3,4-oxadiazoles with acid chlorides is catalyzed by N,N-dimethyl-4-aminopyridine (DMAP) and affords the corresponding 2-ketoazoles in good yields.
P. Lassalas, F. Marsais, C. Hoarau, Synlett, 2013, 24, 2233-2240.
A "bulky-yet-flexible" Pd-PEPPSI-IPentAn complex catalyzes a highly efficient amination of sterically hindered (hetero)aryl chlorides with a variety of aliphatic and aromatic amines. The operationally simple protocol smoothly proceeded under mild conditions without the exclusion of air and moisture to provide the desired products.
F.-D. Huang, C. Xu, D.-D. Lu, D.-S. Shen, T. Li, F.-S. Liu, J. Org. Chem., 2018, 83, 9144-9155.