Grantee Research Project Results
Final Report: Carbon-Carbon Bond Formations in Water and Other Alternative Media
EPA Grant Number: R831662Title: Carbon-Carbon Bond Formations in Water and Other Alternative Media
Investigators: Li, Chao-Jun
Institution: Tulane University
EPA Project Officer: Richards, April
Project Period: June 1, 2004 through June 1, 2008
RFA: Technology for a Sustainable Environment (2003) RFA Text | Recipients Lists
Research Category: Pollution Prevention/Sustainable Development , Sustainable and Healthy Communities
Objective:
The overall objective of this research is to explore novel chemical reactivities for more efficient and environmentally benign chemical synthesis in cleaner reaction media. In particular, the research is directed towards novel C-C bond formation reactions, the essence of chemical syntheses.
Summary/Accomplishments (Outputs/Outcomes):
During the funding period, we have accomplished fundamental scientific advance in four major parts:
- Studies of greener media for catalytic reactions and synthesis. We have studied various transition-metal catalyzed carbon-carbon bond formations and related reactions in water, ionic liquids, and solventless conditions. Research activities have been focused on palladium catalyzed reaction of terminal alkynes in water and precious metal catalyzed reaction of alkynes in water and ionic liquids. In particular, we have further investigated the A3 coupling (aldehyde-alkyne-amine coupling) developed by us. We have also further investigated the asymmetric version of this reaction. Different catalysts showed complementary chemoselectivities. Palladium catalyzed addition of terminal alkynes to electron-difficient alkenes was discovered for the first time in water during this period. Palladium-catalyzed coupling of terminal alkynes and acid chloride in water was also discovered for the first time.
- Studies on direct coupling of C-H and C-H bond under neat conditions and without using metal catalyst. Traditional organic synthesis requires the use of functional groups. As a potentially new strategy to go beyond functionalization and defunctionalization, we have developed a wide range of new C-C bond formation reaction termed as Cross-Dehydrogenative-Coupling (CDC) by us. Such reactions provide the most direct and efficient way to connect molecules.
- An efficient method for green separation of products from reactions in water was developed. The advantages of using water as a greener solvent is limited by the difficulty associated with isolating water-soluble products from water. To overcome this problem, we developed novel “fishing” method for isolating products via “flourous tagging”.
- A direct C-C bond formation by using alkanes was developed. Traditionally, alkanes are the most stable compounds and have very little synthetic usage. We discovered several efficient C-C bond formation reactions based on simple alkanes.
The funding allows the generation of a large number of top publications as shown below:
- Luo, Y.; Li, Z.; Li, C.-J. “A Silver-Catalyzed Domino Route toward 1,2-Dihydroquinoline Derivatives from Simple Anilines and Alkynes”, Org. Lett. 2005, 7, 0000.
- Li, C. J. “Organic Reactions in Aqueous Media with a focuse on C-C Bond Formations: a Decade Update”, Chem. Rev. 2005, 0000.
- Jiang, N.; Li, C. J. “Catalysis of Industrial Importance in Aqueous Media” chapter in Environmental Catalysis, CRC Press, Boca Raton, 2005, P 591-608.
- Wei, C.; Li, C. J. “Gold-Catalyzed Coupling of Alkynes and Acyl Iminiums”, Lett. Org. Chem. 2005, 2, 0000.
- Keh, C. C. K.; Li, C. J. “Atom-Economy”, McGraw-Hill Yearbook of Scienec and Technology, 2005, 21.
- Zhang, Y.; Li, C. J. “Microwave-Assisted Direct Addition of Cycloethers to Alkynes”, Tetrahedron Lett. 2004, 45, 7581-7584.
- Chen, L.; Li, C. J. “The First Palladium-catalyzed 1,4-Addition of Terminal Alkynes to Conjugated Enones”, Chem. Commun. 2004, 2362-2364.
- Chen, L.; Li, C. J. “A Remarkably Efficient Coupling of Acid Chlorides with Alkynes in Water”, Org. Lett. 2004, 6, 3151-3153.
- Wei, C.; Mague, J. T.; Li, C. J. “Cu(I)-Catalyzed Direct Addition and Asymmetric Addition of Terminal Alkynes to Imines.” Proc. Natl. Acad. Sci. (USA), 2004, 101, 5749-5754.
- Luo, Y.; Li, C. J. “A Highly Efficient Gold/Silver-Catalyzed Addition of Arenes to Imines” Chem. Commun. 2004, 1930-1931.
- Yang, X. F.; Wang, M.; Varma, R. S.; Li, C. J. “Ruthenium-Catalyzed Tandem Olefin Migration–Aldol and Mannich-Type Reactions in Ionic Liquid” J. Mol. Catal. A. 2004, 214, 147-154.
- Chen, L.; Li, C. J. “Facile and selective copper-palladium catalyzed addition of terminal alkynes to activated alkynes in water”, Tetrahedron Lett. 2004, 45, 2771-2774.
- Li, Z.; Wei, C.; Chen, L.; Varma, R. S.; Li, C. J. “Three component coupling of aldehyde, alkyne and amine catalyzed by silver in ionic liquid”, Tetrahedron Lett. 2004, 45, 2443-2446.
- Jiang, N; Li, C. J. “Novel 1,3-Dipolar Cycloaddition of Diazocarbonyl Compounds to Alkynes in Water “ Chem. Commun. 2004, 394-395.
- Wu, W.; Li, C. J. “Tandem Rhodium-Catalyzed Alkyne Hydrostannylation-Conjugated Additions in Water” invited article, Lett. Org. Chem., 2004, 1, 122-124.
- Wang, M.; Li, C. J. “Ruthenium-Catalyzed Organic Synthesis in Aqueous Media” invited chapter, in Topics in Organomet. Chem. 2004, 11, 321-336; Springer-Verlag Berlin Heidelberg 2004.
- Wei, C.; Li, Z.; Li, C. J. ”The Development of A3-Coupling (Aldehyde-Alkyne-Amine) and AA3-Coupling (Asymmetric Aldehyde-Alkyne-Amine” (Invited Account) Synlett 2004,1472-1483.
Journal Articles on this Report : 27 Displayed | Download in RIS Format
| Other project views: | All 138 publications | 29 publications in selected types | All 27 journal articles |
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Chen L, Li C-J. Facile and selective copper--palladium catalyzed addition of terminal alkynes to activated alkynes in water. Tetrahedron Letters 2004;45(13):2771-2774. |
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Chen L, Li C-J. The first palladium-catalyzed 1,4-addition of terminal alkynes to conjugated enones. Chemical Communications 2004;(20):2362-2364. |
R831662 (Final) R828129 (2002) |
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Chen L, Li C-J. A remarkably efficient coupling of acid chlorides with alkynes in water. Organic Letters 2004;6(18):3151-3153. |
R831662 (Final) R828129 (2002) |
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Deng G, Zhao L, Li C-J. Ruthenium-catalyzed oxidative cross-coupling of chelating arenes and cycloalkanes. Angewandte Chemie International Edition 2008;47(33):6278-6282. |
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Deng G, Chen W, Li C-J. An unusual peroxide-mediated amination of cycloalkanes with nitroarenes. Advanced Synthesis & Catalysis 2009;351(3):353-356. |
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Deng G, Ueda K, Yanagisawa S, Itami K, Li C-J. Coupling of nitrogen heteroaromatics and alkanes without transition metals: a new oxidative cross-coupling at C--H/C--H Bonds.Chemistry: A European Journal 2009;15(2):333-337. |
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Jiang N, Li C-J. Novel 1,3-dipolar cycloaddition of diazocarbonyl compounds to alkynes catalyzed by InCl3 in water. Chemical Communications 2004;(4):394-395. |
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Li C-J. Organic reactions in aqueous media with a focus on carbon-carbon bond formations:a decade update. Chemical Reviews 2005;105(8):3095-3165. |
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Li C-J, Chen L. Organic chemistry in water. Chemical Society Reviews 2006;35(1):68-82. |
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Li C-J. Cross-dehydrogenative coupling (CDC): exploring C-C bond formations beyond functional group transformations. Accounts of Chemical Research 2009;42(2):335-344. |
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Li C-J. The development of catalytic nucleophilic additions of terminal alkynes in water. Accounts of Chemical Research 2010;43(4):581-590. |
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Li C-J. Unorthodox chemistry for an unorthodox challenge: exploration of new chemical reactivities for a sustainable future. Science China Chemistry 2011;54(12):1815-1830. |
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Luo Y, Li C-J. A highly efficient gold/silver-catalyzed addition of arenes to imines. Chemical Communications 2004;(17):1930-1931. |
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Luo Y, Li Z, Li C-J. A silver-catalyzed domino route toward 1,2-dihydroquinoline derivatives from simple anilines and alkynes.Organic Letters 2005;7(13):2675-2678. |
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Wei C, Li Z, Li C-J. The development of A3-coupling (aldehyde-alkyne-amine) and AA3-coupling (asymmetric aldehyde-alkyne-amine). Synlett 2004;(9):1472-1483. |
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Wei C, Li C-J. Gold-catalyzed coupling of alkynes and acyl iminiums. Letters in Organic Chemistry 2005;2(5):410-414. |
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Wei W, Keh CCK, Li C-J, Varma RS. Water as a reaction medium for clean chemical processes. Clean Technologies and Environmental Policy 2004;6(4):250-257. |
R831662 (Final) R828129 (2002) |
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Wu W, Li C-J. A one-pot, rhodium-catalyzed hydrostannylation-conjugate addition in air and water. Letters in Organic Chemistry 2004;1(2):122-124. |
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Yang X-F, Wang M, Varma RS, Li C-J. Ruthenium-catalyzed tandem olefin migration--aldol- and Mannich-type reactions in ionic liquid. Journal of Molecular Catalysis A: Chemical 2004;214(1):147-154. |
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Yang X-F, Wang M, Zhang Y, Li C-J. 2, 4-diaryltetrahydropyran formation by the Prins cyclization and its application towards the synthesis of epicalyxin F and calyxin I. Synlett 2005;(12):1912-1916. |
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Yoo W-J, Correia CA, Zhang Y, Li C-J. Oxidative alkylation of cyclic benzyl ethers with malonates and ketones using oxygen as the terminal oxidant. Synlett 2009;(1):138-142. |
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Zhang Y, Li C-J. Microwave-assisted direct addition of cycloethers to alkynes. Tetrahedron Letters 2004;45(41):7581-7584. |
R831662 (Final) R828129 (2002) |
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Zhang Y, Li C-J. DDQ-mediated direct cross-dehydrogenative-coupling (CDC) between benzyl ethers and simple ketones. Journal of the American Chemical Society 2006;128(13):4242-4243. |
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Zhang Y, Li C-J. Highly efficient cross-dehydrogenative-coupling between ethers and active methlyene compounds. Angewandte Chemie International Edition 2006;45(12):1949-1952. |
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Zhang Y, Donahue JP, Li C-J. Gold(III)-catalyzed double hydroamination of o-alkynylaniline with terminal alkynes leading to N-vinylindoles. Organic Letters 2007;9(4):627-630. |
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Zhang Y, Feng J, Li C-J. Palladium-catalyzed methylation of aryl C-H bond by using peroxides. Journal of the American Chemical Society 2008;130(10):2900-2901. |
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Zhou L, Chen L, Skouta R, Jiang Hf, Li C-J. Palladium-catalyzed 1,4-addition of terminal alkynes to unsaturated carbonyl compounds promoted by electron-rich ligands. Organic & Biomolecular Chemistry 2008;6(16):2969-2977. |
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Supplemental Keywords:
C-C Bond Formation, Cleaner Reaction Media, Cleaner Synthesis,, Sustainable Industry/Business, cleaner production/pollution preventionRelevant Websites:
http://cjli.mcgill.ca/ ExitProgress and Final Reports:
Original AbstractThe perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Conclusions drawn by the principal investigators have not been reviewed by the Agency.