Polyethylene Glycol–Enhanced Chemoselective Synthesis of Organic Carbamates from Amines, CO₂, and Alkyl Halides

REFERENCES

• For selected examples using carbamates as biologically active compounds in the field of pharmaceuticals , see Goodman , L. ; Gilman , A. ; Rall , T. W. ; Nies , A. S. ; Taylor , P. The Pharmacological Basis of Therapeutics, , 8th ed. ; Pergamon Press : New York , 1990 .
   Google Scholar
• For selected examples using carbamates as biologically active compounds in the field of agriculture, see (a) Kato , T. ; Suzuki , K. ; Takahashi , J. ; Kamoshita , K. Hyperammonemia in lysinuric protein intolerance . J. Pesticide Sci. 1984 , 9 , 489 – 492 ; (b) Tai-The , W. ; Huang , J. ; Arrington , N. D. ; Dill , G. M. Synthesis and herbicidal activity of α-heterocyclic carbinol carbamates . J. Agric. Food Chem. 1987 , 35 , 817 – 823 ; (c) Rivetti , F. ; Romano , U. ; Sasselli , M. U.S. Patent 4514339, ECS, 1985.
   Web of Science ®Google Scholar
• For selected examples using carbamates as key intermediates or as protecting groups, see (a) Greene , T. W. ; Wuts , P. G. M. Protective Groups in Organic Synthesis, 3rd ed. ; Wiley: New York, 1999; (b) Connolly , T. J. ; Crittall , A. J. ; Ebrahim , A. S. ; Ji , G. Development and scale up of a route to cyclohexylhydrazine dimethanesulfonate . Org. Process Res. Dev. 2000 , 4 , 526 – 529 .
   Google Scholar
• Aresta , M. ; Quaranta , E. Role of the macrocyclic polyether in the synthesis of N-alkylcarbamate esters from primary amines, CO2, and alkyl halides in the presence of crownethers . Tetrahedron 1992 , 48 , 1515 – 1530 .
   Web of Science ®Google Scholar
• For selected examples for condensation of amines with CO2 to afford ureas, see (a) Fournier , J. ; Bruneau , C. ; Dixneuf , P. H. ; Lgcolier , S. Ruthenium-catalyzed synthesis of symmetrical N,N'-dialkylureas directly from carbon dioxide and amines . J. Org. Chem. 1991 , 56 , 4456 – 4458 ; (b) Nomura , R. ; Hasegawa , Y. ; Ishimoto , M. ; Toyosaki , T. ; Matsuda , H. Carbonylation of amines by carbon dioxide in the presence of an organoantimony catalyst . J. Org. Chem. 1992 , 57 , 7339 – 7342 ; (c) Tai , C.-C. ; Huck , M. J. ; McKoon , E. P. ; Woo , T. ; Jessop , P. G. Low-temperature synthesis of tetraalkylureas from secondary amines and carbon dioxide . J. Org. Chem. 2002 , 67 , 9070 – 9072 ; (d) Shi , F. ; Deng , Y. ; SiMa , T. ; Peng , J. ; Gu , Y. ; Qiao , B. Alternatives to phosgene and carbon monoxide: Synthesis of symmetric urea derivatives with carbon dioxide in ionic liquids . Angew. Chem. Int. Ed. 2003 , 42 , 3257 – 3260 ; (e) Munshi , P. ; Heldebrant , D. J. ; McKoon , E. P. ; Kelly , P. A. ; Tai , C.-C. ; Jessop , P. G. Formanilide and carbanilide from aniline and carbon dioxide . Tetrahedron Lett. 2003 , 44 , 2725 – 2727 ; (f) Porwanski , S. ; Menuel , S. ; Marsura , X. ; Marsura , A. The modified “phosphine imide” reaction: A safe and soft alternative ureas synthesis . Tetrahedron Lett. 2004 , 45 , 5027 – 5029 ; (g) Shi , F. ; Zhang , Q. ; Ma , Y. ; He , Y. ; Deng , Y. From CO oxidation to CO2 activation: An unexpected catalytic activity of polymer-supported nanogold . J. Am. Chem. Soc. 2005 , 127 , 4182 – 4183 ; (h) Ion , A. ; Parvulescu , V. ; Jacobs , P. ; Vos , D. D. Synthesis of symmetrical or asymmetrical urea compounds from CO2 via base catalysis . Green Chem. 2007 , 9 , 158 – 161 ; (i) Jiang , T. ; Ma , X. ; Zhou , Y. ; Liang , S. ; Zhang , J. ; Han , B. Solvent-free synthesis of substituted ureas from CO2 and amines with a functional ionic liquid as the catalyst . Green Chem. 2008 , 10 , 465 – 469 .
   Web of Science ®Google Scholar
• For selected examples for condensation of amine with carbon dioxide and halide in the present of Cs2CO3 to afford carbamate, see (a) Salvatore , R. N. ; Flanders , V. L. ; Ha , D. ; Jung , K. W. Cs2CO3-promoted efficient carbonate and carbamate synthesis on solid phase . Org. Lett. 2000 , 2 , 2797 – 2800 ; (b) Salvatore , R. N. ; Shin , S. I. ; Nagle , A. S. ; Jung , K. W. Efficient carbamate synthesis via a three-component coupling of an amine, CO2, and alkyl halides in the presence of Cs2CO3 and tetrabutylammonium iodide . J. Org. Chem. 2001 , 66 , 1035 – 1037 ; (c) Salvatore , R. N. ; Ledger , J. A. ; Jung , K. W. An efficient one-pot synthesis of N-alkyl carbamates from primary amines using Cs2CO3 . Tetrahedron Lett. 2001 , 42 , 6023 – 6025 ; (d) Salvatore , R. N. ; Chu , F. ; Nagle , A. S. ; Kapxhiu , E. A. ; Cross , R. M. ; Jung , K. W. Efficient Cs2CO3-promoted solution and solid-phase synthesis of carbonates and carbamates in the presence of TBAI . Tetrahedron 2002 , 58 , 3329 – 3347 ; (e) Fox , D. L. ; Ruxer , J. T. ; Oliver , J. M. ; Alford , K. L. ; Salvatore , R. N. Mild and efficient synthesis of carbazates and dithiocarbazates via a three-component coupling using Cs2CO3 and TBAI . Tetrahedron Lett. 2004 , 45 , 401 – 405 .
   PubMed Web of Science ®Google Scholar
• For selected examples for condensation of amine with CO2 and halide in the presence of organic bases to afford carbamate, see (a) McGhee , W. D. ; Pan , Y. ; Riley , D. P. Highly selective generation of urethanes from amines, carbon dioxide, and alkyl chlorides. J. Chem. Soc., Chem. Commun. 1994, 699–700; (b) McGhee , W. D. ; Riley , D. P. ; Christ , K. ; Pan , Y. ; Parnas , B. Carbon dioxide as a phosgene replacement: Synthesis and mechanistic studies of urethanes from amines, CO2, and alkyl chlorides. J. Org. Chem. 1995, 60, 2820–2830.
   Google Scholar
• Yoshida , M. ; Hara , N. ; Okuyama , S. Catalytic production of urethanes from amines and alkyl halides in supercritical carbon dioxide . Chem. Commun. 2000 , 151 – 152 .
   Web of Science ®Google Scholar
• For selected examples for condensation of amine with CO2 and alcohol in the presence of dehydrating agents to afford carbamate, see (a) Abla , M. ; Choi , J.-C. ; Sakakura , T. Halogen-free process for the conversion of carbon dioxide to urethanes by homogeneous catalysis . Chem. Commun. 2001 , 2238 – 2239 ; (b) Chaturvedi , D. ; Kumar , A. ; Ray , S. A high–yielding, one-pot, novel synthesis of carbamate esters from alcohols using Mitsunobu's reagent . Tetrahedron Lett. 2003 , 44 , 7637 – 7639 ; (c) Ion , A. ; Doorslaer , C. V. ; Parvulescu , V. ; Jacobsa , P. ; Vos , D. D. Green synthesis of carbamates from CO2, amines, and alcohols . Green Chem. 2008 , 10 , 111 – 116 .
   Web of Science ®Google Scholar
• Chen , J. ; Spear , S. K. ; Huddleston , J. G. ; Rogers , R. D. Polyethylene glycol and solutions of polyethylene glycol as green reaction media . Green Chem. 2005 , 7 , 64 – 82 .
   Web of Science ®Google Scholar
• Ottani , S. ; Vitalini , D. ; Comelli , F. ; Castellari , C. Densities, viscosities, and refractive indices of poly(ethylene glycol) 200 and 400 + cyclic ethers at 303.15 K . J. Chem. Eng. Data 2002 , 47 , 1197 – 1204 .
   Web of Science ®Google Scholar
• Cortright , R. D. ; Sanchez-Castillo , M. ; Dumesic , J. A. Conversion of biomass to 1,2-propanediol by selective catalytic hydrogenation of lactic acid over silica-supported copper . Appl. Catal., B: Environ. 2002 , 39 , 353 – 359 .
   Web of Science ®Google Scholar
• (a) Naik , S. D. ; Doraiswamy , L. K. Phase transfer catalysis: Chemistry and engineering . AIChE J. 1998 , 44 , 612 – 646 ; (b) Guo , Z. ; Li , M. ; Willauer , H. D. ; Huddleston , J. G. ; April , G. C. ; Rogers , R. D. Evaluation of polymer-based aqueous biphasic systems as improvement for the hardwood alkaline pulping process . Ind. Eng. Chem. Res. 2002 , 41 , 2535 – 2542 ; (c) Chen , J. ; Spear , S. K. ; Huddleston , J. G. ; Holbrey , J. H. ; Swatloski , R. P. ; Rogers , R. D. Application of poly(ethylene glycol)-based aqueous biphasic systems as reaction and reactive extraction media . Ind. Eng. Chem. Res. 2004 , 43 , 5358 – 5364 ; (d) Chen , J. ; Spear , S. K. ; Huddleston , J. G. ; Holbrey , J. H. ; Rogers , R. D. Application of polyethylene glycol-based aqueous biphasic reactive extraction to the catalytic oxidation of cyclic olefins . J. Chromatogr. B 2004 , 807 , 145 – 149 .
   Web of Science ®Google Scholar
• Totten , G. E. ; Clinton , N. A. ; Matlock , P. L. Poly(ethylene glycol) and derivatives as phase transfer catalysts . J. Macromol. Sci. Rev. Macromol. Chem. Phys. 1998 , C38 , 77 – 142 .
   Web of Science ®Google Scholar
• For examples of the use of PEG as reaction media in organic synthesis, see (a) Harris , J. M. ; Hundley , N. H. ; Shannon , T. G. ; Struck , E. C. In Crown Ethers and Phase-Transfer Catalysis in Polymer Science ; L. J. Mathias and C. E. Carraher Jr. (Eds.); Plenum Press : New York , 1984 ; pp. 371 ; (b) Totten , G. E. ; Clinton , N. A. Poly[ethylene glycol] derivatives as phase-transfer catalysts and solvents for organic reactions. J. Macromol. Sci. Rev. Macromol. Chem. Phys. 1988, C28, 293–337 ; (c) Starks , C. M. ; Liotta , C. L. ; Halpern , M. Phase-Transfer Catalysis: Fundamentals, Applications and Industrial Perspectives ; Chapman & Hall : New York , 1994 ; p. 158 ; (d) Li , J.-H. ; Liu , W.-J. ; Xie , Y.-X. Recyclable and reusable Pd(OAc)2/DABCO/PEG-400 system for Suzuki−Miyaura cross-coupling reaction. J. Org. Chem. 2005, 70, 5409–5412 ; (e) Zhang , Z.-H. ; Yin , L. ; Wang , Y.-M. ; Liu , J.-Y. ; Li , Y. Indium tribromide in poly(ethylene glycol) (PEG): A novel and efficient recycle system for chemoselective deprotection of 1,1-diacetates. Green Chem. 2004, 6, 563–565 ; (f) Smith , C. B. ; Raston , C. L. ; Sobolev , A. N. Poly(ethyleneglycol) (PEG): A versatile reaction medium in gaining access to 4-(pyridyl)-terpyridines. Green Chem. 2005, 7, 650–654 ; (g) Jain , S. L. ; Singhal , S. ; Sain , B. PEG-assisted solvent and catalyst-free synthesis of 3,4-dihydropyrimidinones under mild reaction conditions. Green Chem. 2007, 9, 740–741 ; (h) Mao , J. ; Guo , J. ; Fang , F. ; Ji , S.-J. Highly efficient copper(0)-catalyzed Suzuki–Miyaura cross-coupling reactions in reusable PEG-400. Tetrahedron 2008, 64, 3905–3911; (i) Kouznestsov , V. V. ; Arenas , D. R. M. First green protocols for the large-scale preparation of γ-diisoeugenol and related dihydro(1H)indenes via formal [3 + 2] cycloaddition reactions. Tetrahedron Lett. 2009, 50, 1546–1549 .
   Google Scholar
• Abribat , B. ; Bigot , Y. L. ; Gaset , A. Etherification of alcohols in the absence of solvent: Catalytic function of polyethers in a solid/liquid medium. Synth. Commun. 1994, 24, 2091–2096.
   Web of Science ®Google Scholar
• de Boer , J. A. A. ; Reinhoudt , D. N. Complexation of tert-butylammonium perchlorate by crown ethers in polar solvents studied by proton NMR spectroscopy . J. Am. Chem. Soc. 1985 , 107 , 5347 – 5351 .
   Web of Science ®Google Scholar
• (a) Wang , J.-Q. ; He , L.-N. ; Miao , C.-X. ; Gao , J. The free-radical chemistry of polyethylene glycol: Organic reactions in compressed carbon dioxide . ChemSusChem 2009 , 2 , 755 – 760 ; (b) Wang , J.-Q. ; He , L.-N. ; Miao , C.-X. Polyethylene glycol radical–initiated oxidation of benzylic alcohols in compressed carbon dioxide . Green Chem. 2009 , 11 , 1013 – 1017 ; (c) Wang , J.-L. ; He , L.-N. ; Dou , X.-Y. ; Wu , F. Poly(ethylene glycol): An alternative solvent for the synthesis of cyclic carbonate from vicinal halohydrin and carbon dioxide . Aus. J. Chem. 2009 , 62 , 917 – 920 ; (d) Du , Y. ; Wu , Y. ; Liu , A.-H. ; He , L.-N. Quaternary ammonium bromide functionalized polyethylene glycol: A highly efficient and recyclable catalyst for selective synthesis of 5-aryl-2-oxazolidinones from carbon dioxide and aziridines under solvent-free conditions . J. Org. Chem. 2008 , 73 , 4709 – 4712 ; (e) Wang , J.-Q. ; Cai , F. ; Wang , E. ; He , L.-N. Supercritical carbon dioxide and poly(ethylene glycol): An environmentally benign biphasic solvent system for aerobic oxidation of styrene . Green. Chem. 2007 , 9 , 882 – 887 ; (f) Tian , J.-S. ; Maio , C.-X. ; Wang , J.-Q. ; Cai , F. ; Du , Y. ; Zhao , Y. ; He , L.-N. Efficient synthesis of dimethyl carbonate from methanol, propylene oxide, and CO2 catalyzed by recyclable inorganic base/phosphonium halide-functionalized polyethylene glycol . Green Chem. 2007 , 9 , 566 – 571 ; (g) Dou , X.-Y. ; Wang , J.-Q. ; Wang , E. ; He , L.-N. Guanidinium salt functionalized PEG: An effective and recyclable homogeneous catalyst for the synthesis of cyclic carbonates from CO2 and epoxides under solvent-free conditions . Synlett 2007 , 19 , 3058 – 3062 ; (h) Du , Y. ; Wang , J.-Q. ; Chen , J.-H. ; Cai , F. ; Tian , J.-S. ; Kong , D.-L. ; He , L.-N. A poly(ethylene glycol)–supported quaternary ammonium salt for highly efficient and environmentally friendly chemical fixation of CO2 with epoxides under supercritical conditions . Tetrahedron Lett. 2006 , 47 , 1271 – 1275 ; (i) Kong , D.-L. ; He , L.-N. ; Wang , J.-Q. Synthesis of urea derivatives from CO2 and amines catalyzed by polyethylene glycol–supported potassium hydroxide without dehydrating agents . Synlett 2010 , 1276 – 1280 .
   PubMed Web of Science ®Google Scholar
• (a) McGhee , W. ; Riley , D. ; Christ , K. ; Pan , Y. ; Parnas , B. Carbon dioxide as a phosgene replacement: Synthesis and mechanistic studies of urethanes from amines, CO2, and alkyl chlorides . J. Org. Chem. 1995 , 60 , 2820 – 2830 ; (b) Yamada , H. ; Wada , Y. ; Tanimoto , S. ; Okano , M. The reaction of isocyanides with halogens or N-halosuccinimides and alcohols . Bull. Chem. Soc. Jpn. 1982 , 55 , 2480 – 2483 .
   Web of Science ®Google Scholar