Isolation and reactivity of trifluoromethyl iodonium salts

ACS Central Science

Volumn 2, Issue 5, 2016, Pages 341-350

  Brantley, Johnathan N ^a   Samant, Andrew V ^a   Toste, F Dean ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BIOCHEMISTRY;

AMBIENT CONDITIONS; ELECTROPHILIC TRIFLUOROMETHYLATION; HYPERVALENT IODINE REAGENTS; MECHANISTIC PROBES; METABOLIC STABILITY; MOLECULAR ARCHITECTURE; PHYSICOCHEMICAL PROPERTY; TRIFLUOROMETHYLATION;

SALTS;

EID: 85014161985     PISSN: 23747943     EISSN: 23747951     Source Type: Journal    
DOI: 10.1021/acscentsci.6b00119     Document Type: Article

References (45)

1. Furuya, T.; Kamlet, A. S.; Ritter, T. Catalysis for fluorination of trifluoromethylation. Nature 2011, 473, 470-477.
2. Liang, T.; Neumann, C. N.; Ritter, T. Introduction of fluorine and fluorine-containing functional groups. Angew. Chem., Int. Ed. 2013, 52, 8214-8264.
3. Egami, H.; Sodeoka, M. Trifluoromethylation of alkenes with concomitant introduction of additional functional groups. Angew. Chem., Int. Ed. 2014, 53, 8294-8308.
4. Merino, E.; Nevado, C. Addition of CF3 across unsaturated moieties: a powerful functionalization tool. Chem. Soc. Rev. 2014, 43, 6598-6608.
5. Rivkin, A.; Chou, T.-C.; Danishefsky, S. J. On the remarkable antitumor properties of fludelone: how we got there. Angew. Chem., Int. Ed. 2005, 44, 2838-2850.
6. Brand, J. P.; Fernández González, D.; Nicolai, S.; Waser, J. Benziodoxole-based hypervalent iodine reagents for atom transfer reactions. Chem. Commun. 2011, 47, 102-115.
7. Eisenberger, P.; Gischig, S.; Togni, A. Novel 10-I-3 hypervalent iodine-based compounds for electrophilic trifluoromethylation. Chem. - Eur. J. 2006, 12, 2579-2586.
8. Eisenberger, P.; Kieltsch, I.; Koller, R.; Stanek, K.; Togni, A. Preparation of a trifluoromethyl transfer agent: 1-trifluromethyl-1, 3- dihydro-3, 3-dimethyl-1, 2-benziodoxole. Org. Synth. 2011, 88, 168.
9. Matoušek, V.; Pietrasiak, E.; Schwenk, R.; Togni, A. One-pot synthesis of hypervalent iodine reagents for electrophilic trifluoromethylation. J. Org. Chem. 2013, 78, 6763-6768.
10. Charpentier, J.; Früh, N.; Togni, A. Electrophilic trifluoromethylation by use of hypervalent iodine reagents. Chem. Rev. 2015, 115, 650-682.
11. Stanek, K.; Koller, R.; Togni, A. Reactivity of a 10-I-3 hypervalent iodine trifluoromethylation reagent with phenols. J. Org. Chem. 2008, 73, 7678-7685.
12. Koller, R.; Stanek, K.; Stolz, D.; Aardoom, R.; Niedermann, K.; Togni, A. Zinc-mediated formation of trifluoromethyl ethers from alcohols and hypervalent iodine trifluoromethylation reagents. Angew. Chem., Int. Ed. 2009, 48, 4332-4336.
13. Koller, R.; Huchet, Q.; Battaglia, P.; Welch, J. M.; Togni, A. Acid-mediated formation of trifluoromethyl sulfonates from sulfonic acids and a hypervalent iodine trifluoromethylating agent. Chem. Commun. 2009, 40, 5993-5995.
14. Kieltsch, I.; Eisenberger, P.; Togni, A. Mild electrophilic trifluoromethylation of carbon- and sulfur-centered nucleophiles by a hypervalent iodine(III)-CF3 reagent. Angew. Chem., Int. Ed. 2007, 46, 754-757.
15. Eisenberger, P.; Kieltsch, I.; Armanino, N.; Togni, A. Mild electrophilic trifluoromethylation of secondary and primary aryl- and alkylphosphine using hypervalent iodine(III)-CF3 reagents. Chem. Commun. 2008, 13, 1575-1577.
16. Charkoudian, L. K.; Liu, C. W.; Capone, S.; Kapur, S.; Cane, D. E.; Togni, A.; Seebach, D.; Khosla, C. Probing the interactions of an acyl carrier protein domain from the 6-deoxyerythronolide B synthase. Protein Sci. 2011, 20, 1244-1255.
17. Mejía, E.; Togni, A. Rhenium-catalyzed trifluoromethylation of arenes and heteroarenes by hypervalent iodine reagents. ACS Catal. 2012, 2, 521-527.
18. Santschi, N.; Togni, A. Electrophilic trifluoromethylation of Shydrogen phosphorothioates. J. Org. Chem. 2011, 76, 4189-4193.
19. Niedermann, K.; Früh, N.; Senn, R.; Czarniecki, B.; Verel, R.; Togni, A. Direct N-trifluoromethylation of azoles by a hypervalent iodine reagent. Angew. Chem., Int. Ed. 2012, 51, 6511-6515.
20. Niedermann, K.; Früh, N.; Vinogradova, E.; Wiehn, M. S.; Moreno, A.; Togni, A. A Ritter-type reaction: direct electrophilic trifluoromethylation at nitrogen atoms using hypervalent iodine reagents. Angew. Chem., Int. Ed. 2011, 50, 1059-1063.
21. Matoušek, V.; Pietrasiak, E.; Sigrist, L.; Czarniecki, B.; Togni, A. O-trifluoromethylation of N, N-disubstituted hydroxylamines with hypervalent iodine reagents. Eur. J. Org. Chem. 2014, 2014, 3087-3092.
22. Lin, X.; Wang, G.; Li, H.; Huang, Y.; He, W.; Ye, D.; Huang, K.-W.; Yuan, Y.; Weng, Z. Copper-catalyzed trifluoromethylation of aryl sulfinate salts using an electrophilic trifluoromethylation reagent. Tetrahedron 2013, 69, 2628-2632.
23. Fauster, K.; Kreutz, C.; Micura, R. 2'-SCF3 uridine - a powerful label for probing structure and function of RNA by 19F NMR spectroscopy. Angew. Chem., Int. Ed. 2012, 51, 13080-13084.
24. Egami, H.; Kawamura, S.; Miyazaki, A.; Sodeoka, M. Trifluoromethylation reactions for the synthesis of β-trifluoromethylamines. Angew. Chem., Int. Ed. 2013, 52, 7841-7844.
25. Mizuta, S.; Engle, K. M.; Verhoog, S.; Galicia-López, O.; O'Duill, M.; Médebielle, M.; Wheelhouse, K.; Rassias, G.; Thompson, A. L.; Gouverneur, V. Trifluoromethylation of allylsilanes under photoredox catalysis. Org. Lett. 2013, 15, 1250-1253.
26. Weng, Z.; Li, H.; He, W.; Yao, L.-F.; Tan, J.; Chen, J.; Yuan, Y.; Huang, K.-W. Mild copper-catalyzed trifluoromethylation of terminal alkynes using an electrophilic trifluoromethylating reagent. Tetrahedron 2012, 68, 2527-2531.
27. Cai, S.; Chen, C.; Sun, Z.; Xi, C. CuCl-catalyzed ortho trifluoromethylation of arenes and heteroarenes with a pivalamido directing group. Chem. Commun. 2013, 49, 4552-4554.
28. Shimizu, R.; Egami, H.; Nagi, T.; Chae, J.; Hamashima, Y.; Sodeoka, M. Direct C2-trifluoromethylation of indole derivatives catalyzed by copper acetate. Tetrahedron Lett. 2010, 51, 5947-5949.
29. Allen, A. E.; Macmillan, D. W. C. The productive merger of iodonium salts and organocatalysis: a non-photolytic approach to the enantioselective alpha-trifluoromethylation of aldehydes. J. Am. Chem. Soc. 2010, 132, 4986-4987.
30. Xu, C.; Liu, J.; Ming, W.; Liu, Y.; Liu, J.; Wang, M.; Liu, Q. In situ generation of Ph(I)+CF3 and transition-metal-free oxidative sp2 CH trifluoromethylation. Chem. - Eur. J. 2013, 19, 9104-9109.
31. Koller, R. Taking electrophilic trifluoromethylation chemistry a step further. ETH Diss. 2010, No. 19219.
32. Umemoto, T.; Kuriu, Y.; Shuyama, H.; Miyano, O.; Nakayama, S.-I. Syntheses and properties of (perfluoroalkyl)phenyliodonium triflates (fits reagents) and their analogues. J. Fluorine Chem. 1986, 31, 37-56.
33. Umemoto, T. Electrophilic perfluoroalkylating agents. Chem. Rev. 1996, 96, 1757-1778.
34. Yagupolskii, L. M. Aromatic compounds with new fluorinecontaining substituents. J. Fluorine Chem. 1987, 36, 1-28.
35. Huheey, E. The electronegativity of groups. J. Phys. Chem. 1965, 69, 3284-3291.
36. Minkwitz, R.; Berkei, M. A new method for preparation and crystal structure of (trifluoromethyl)iodine dichloride. Inorg. Chem. 1999, 38, 5041-5044.
37. Archer, E. M.; van Schalkwyk, T. G. The crystal structure of benzene iododichloride. Acta Crystallogr. 1953, 6, 88-92.
38. Alcock, N. W.; Countryman, R. M. Secondary bonding. Part I. Crystal and molecular structures of diphenyliodonium chloride, bromide, and iodide. J. Chem. Soc., Dalton Trans. 1977, 217-219.
39. The ionic character of iodoniums derived from 1 and 2 was further confirmed using IR spectroscopic analysis and conductivity measurements. For example, the carbonyl stretch of 2·MeCl did not change significantly from the solid state (1727 cm-1) to solutions in either CDCl3 (1729 cm-1) or MeCN (1728 cm-1). This shows that, in solution, the carbonyl is not weakened through interactions with the I(III) center. Conductivity measurements also showed that a MeCN solution of 1·HCl ([1·HCl] = 0.01 M) exhibited a roughly 30-fold increase in conductivity relative to a MeCN solution of 1 ([1] = 0.01 M).
40. Parr, R. G.; Yang, W. Density Funtional Theory of Atoms and Molecules; Oxford University Press: New York, 1989.
41. Becke, A. D. A new mixing of Hartree-Fock and local densityfunctional theories. J. Chem. Phys. 1993, 98, 1372-1377.
42. Gordon, M. S.; Binkley, J. S.; Pople, J. A.; Pietro, W. J.; Hehre, W. J. Self-consistent molecular-orbital methods. 22. Small split-valence basis sets for second-row elements. J. Am. Chem. Soc. 1982, 104, 2797-2803.
43. Engl, P. S.; Senn, R.; Otth, E.; Togni, A. Synthesis and characterization of N-trifluoromethyl N-heterocyclic carbene ligands and their coplexes. Organometallics 2015, 34, 1384-1395.
44. Parsons, A. T.; Buchwald, S. L. Copper-catalyzed trifluoromethylation of unactivated olefins. Angew. Chem., Int. Ed. 2011, 50, 9120-9123.
45. Santschi, N.; Geissbühler, P.; Togni, A. Reactivity of an electrophilic hypervalent iodine trifluoromethylation reagent with hydrogen phosphates - a mechanistic study. J. Fluorine Chem. 2012, 135, 83-86.