Computational SN2-Type Mechanism for the Difluoromethylation of Lithium Enolate with Fluoroform through Bimetallic C−F Bond Dual Activation

Chemistry - A European Journal

Volumn 22, Issue 26, 2016, Pages 8796-8800

  Honda, Kazuya ^a   Harris, Travis V ^b,c   Hatanaka, Miho ^b,d   Morokuma, Keiji ^b   Mikami, Koichi ^a  

^a TOKYO INSTITUTE OF TECHNOLOGY   (Japan)

^b KYOTO UNIVERSITY   (Japan)

^c UNIVERSITY OF PUGET SOUND   (United States)

^d KINKI UNIVERSITY   (Japan)

Author keywords

carbenoids; computational chemistry; fluorine; nucleophilic substitution; reaction mechanisms

Indexed keywords

CARBON; CHEMICAL ACTIVATION; CHEMICAL BONDS; COMPUTATIONAL CHEMISTRY; FLUORINE; OLEFINS; SOLVATION;

ARTIFICIAL FORCES; CARBENOIDS; CARBONYL PRODUCTS; LITHIUM ENOLATES; LITHIUM HEXAMETHYLDISILAZIDE; NUCLEOPHILIC SUBSTITUTIONS; REACTION MECHANISM; SOLVATION MODELS;

LITHIUM COMPOUNDS;

EID: 84970971239     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.201601090     Document Type: Article

References (62)

1. J. Wang, M. Sánchez-Roselló, J. L. Aceña, C. del Pozo, A. E. Sorochinky, S. Fustero, V. A. Solochonok, H. Liu, Chem. Rev. 2014, 114, 2432;
2. P. Kirsch, Modern Fluoroorganic Chemistry: Synthesis Reactivity, Applications, 2nd ed., Wiley-VCH, Weinheim, 2013;
3. K. Uneyama, Organofluorine Chemistry, Blackwell, Oxford, 2006;
4. I. Ojima, Fluorine in Medicinal Chemistry and Chemical Biology, Wiley-Blackwell, Chichester, 2009.
5. G. Theodoridis, Adv. Fluorine Sci. 2006, 2, 121.
6. S. Barata-Vallejo, M. R. Torviso, B. Lantaño, S. M. Bonesi, A. Postigo, J. Fluorine Chem. 2014, 161, 134;
7. I. Kieltsch, P. Eisenberger, A. Togni, Angew. Chem. Int. Ed. 2007, 46, 754;
8. Angew. Chem. 2007, 119, 768;
9. T. Umemoto, S. Ishihara, J. Am. Chem. Soc. 1993, 115, 2156;
10. E. J. Cho, T. D. Senecal, T. Kinzel, Y. Zhang, D. A. Watson, S. L. Buchwald, Science 2010, 328, 1679;
11. D. A. Nagib, D. W. C. MacMillan, Nature 2011, 480, 224;
12. Y. Fujiwara, J. A. Dixon, F. O'Hara, E. D. Funder, D. D. Dixon, R. A. Rodriguez, R. D. Baxter, B. Herlé, N. Sach, M. R. Collins, Y. Ishihara, P. S. Baran, Nature 2012, 492, 95.
13. G. K. S. Prakash, C. Weber, S. Chacko, G. A. Olah, Org. Lett. 2007, 9, 1863;
14. W. Zhang, F. Wang, L. Hu, Org. Lett. 2009, 11, 2109;
15. G. K. S. Prakash, Z. Zhang, F. Wang, C. Ni, G. A. Olah, J. Fluorine Chem. 2011, 132, 792;
16. Y. Fujiwara, J. A. Dixon, R. A. Rodriguez, R. D. Baxter, D. D. Dixon, M. R. Collins, D. G. Blackmond, P. S. Baran, J. Am. Chem. Soc. 2012, 134, 1494;
17. P. S. Fier, J. F. Hartwing, J. Am. Chem. Soc. 2012, 134, 5524.
18. T. Iida, R. Hashimoto, K. Aikawa, S. Ito, K. Mikami, Angew. Chem. Int. Ed. 2012, 51, 9535;
19. Angew. Chem. 2012, 124, 9673;
20. R. Hashimoto, T. Iida, K. Aikawa, S. Ito, K. Mikami, Chem. Eur. J. 2014, 20, 2750;
21. K. Mikami, Y. Tomita, Y. Itoh, Angew. Chem. Int. Ed. 2010, 49, 3819;
22. Angew. Chem. 2010, 122, 3907.
23. D. Seebach, Angew. Chem. Int. Ed. Engl.Angew. Chem. Int. Ed. 1988, 27, 1624;
24. Angew. Chem. 1988, 100, 1685;
25. T. Laube, J. D. Dunitz, D. Seebach, Helv. Chim. Acta 1985, 68, 1373; LDA was reported to inhibit alkylations through Li−N and NH–π interactions.
26. D. B. Collum, A. J. McNeil, A. Ramirez, Angew. Chem. Int. Ed. 2007, 46, 3002;
27. Angew. Chem. 2007, 119, 3060;
28. L. M. Pratt, A. Streitwieser, J. Org. Chem. 2003, 68, 2830;
29. P. F. Godenschwager, D. B. Collum, J. Am. Chem. Soc. 2008, 130, 8726;
30. K. J. Kolonko, D. J. Wherritt, H. J. Reich, J. Am. Chem. Soc. 2011, 133, 16774;
31. O. Larrañaga, A. de Cozar, F. M. Bickelhaupt, R. Zangi, F. P. Cossio, Chem. Eur. J. 2013, 19, 13761; LDA-derived enolates gave tetramers of which the reactivity was less than other oligomers:
32. C. Su, R. Hopson, P. G. Williard, J. Am. Chem. Soc. 2014, 136, 3246;
33. J. Guang, Q. P. Liu, R. Hopson, P. G. Williard, J. Am. Chem. Soc. 2015, 137, 7347.
34. Reviews:
35. H. Amii, K. Uneyama, Chem. Rev. 2009, 109, 2119;
36. A. D. Sun, J. A. Love, Dalton Trans. 2010, 39, 10362;
37. H. Torrens, Coord. Chem. Rev. 2005, 249, 1957;
38. T. Braun, F. Wehmeier, Eur. J. Inorg. Chem. 2011, 613;
39. K. Tamao, K. Sumitani, Y. Kiso, M. Zembayashi, A. Fujioka, S. Kodama, I. Nakajima, A. Minato, M. Kumada, Bull. Chem. Soc. Jpn. 1976, 49, 1958;
40. N. Yoshikai, H. Mashima, E. Nakamura, J. Am. Chem. Soc. 2005, 127, 17978;
41. J. Terao, H. Watabe, N. Kambe, J. Am. Chem. Soc. 2005, 127, 3656;
42. C. Douvris, C. M. Nagaraja, C.-H. Chen, B. M. Foxman, O. V. Ozerov, J. Am. Chem. Soc. 2010, 132, 4946;
43. M. F. Kühnel, D. Lentz, Angew. Chem. Int. Ed. 2010, 49, 2933;
44. Angew. Chem. 2010, 122, 2995;
45. Angew. Chem. 2010, 122, 2995;
46. M. Tobisu, T. Xu, T. Shimasaki, N. Chatani, J. Am. Chem. Soc. 2011, 133, 19505;
47. M. Ohashi, T. Kambara, T. Hatanaka, H. Saijo, R. Doi, S. Ogoshi, J. Am.Chem. Soc. 2011, 133, 3256;
48. O. Allemann, S. Duttwyler, P. Romanato, K. K. Baldridge, J. S. Siegel, Science 2011, 332, 574;
49. J. Choi, D. Y. Wang, S. Kundu, Y. Choliy, T. J. Emge, K. K. -Jespersen, A. S. Goldman, Science 2011, 332, 1545.
50. S. Maeda, K. Morokuma, J. Chem. Phys. 2010, 132, 241102;
51. S. Maeda, K. Morokuma, J. Chem. Theory Comput. 2011, 7, 2335;
52. S. Maeda, K. Ohno, K. Morokuma, Phys. Chem. Chem. Phys. 2013, 15, 3683.
53. A. D. Becke, J. Chem. Phys. 1993, 98, 5648.
54. S. Grimme, S. Ehrlich, L. Goerigk, J. Comput. Chem. 2011, 32, 1456.
55. E. Cancès, B. Mennucci, J. Tomasi, J. Chem. Phys. 1997, 107, 3032.
56. A. V. Marenich, C. J. Cramer, D. G. Trhlar, J. Phys. Chem. B 2009, 113, 6378.
57. C. P. Kelly, C. J. Cramer, D. G. Truhlar, J. Phys. Chem. B 2006, 110, 16066.
58. S.Maeda, Y.Harabuchi, Y.Osada, T.Taketsugu, K.Morokuma, K.OhnoGRRM 14:, http://grrm.chem.tohoku.ac.jp/GRRM/ index e.html.
59. RevisionD.M. J.Frisch, G. W.Trucks, H. B.Schlegel, G. E.Scuseria, M. A.Robb, J. R.Cheeseman, G.Scalmani, V.Barone, B.Mennucci, G. A.Petersson, H.Nakatsuji, M.Caricato, X.Li, H. P.Hratchian, A. F.Izmaylov, J.Bloino, G.Zheng, J. L.Sonnenberg, M.Hada, M.Ehara, K.Toyota, R.Fukuda, J.Hasegawa, M.Ishida, T.Nakajima, Y.Honda, O.Kitao, H.Nakai, T.Vreven, J. A.Montgomery, Jr., J. E.Peralta, F.Ogliaro, M.Bearpark, J. J.Heyd, E.Brothers, K. N.Kudin, V. N.Staroverov, R.Kobayashi, J.Normand, K.Raghavachari, A.Rendell, J. C.Burant, S. S.Iyengar, J.Tomasi, M.Cossi, N.Rega, J. M.Millam, M.Klene, J. E.Knox, J. B.Cross, V.Bakken, C.Adamo, J.Jaramillo, R.Gomperts, R. E.Stratmann, O.Yazyev, A. J.Austin, R.Cammi, C.Pomelli, J. W.Ochterski, R. L.Martin, K.Morokuma, V. G.Zakrzewski, G. A.Voth, P.Salvador, J. J.Dannenberg, S.Dapprich, A. D.Daniels, Ö.Farkas, J. B.Foresman, J. V.Ortiz, J.Cioslowski, and D. J.FoxWallingfordCTGaussian 09, 01, Gaussian, Inc., .
60. M. Nakamura, A. Hirai, E. Nakamura, J. Am. Chem. Soc. 2003, 125, 2341, and references therein.
61. C. S. Thomoson, W. R. Dolbier Jr., J. Org. Chem. 2013, 78, 8904; CF3H pKa=27 (in H2O): E. A. Symons, M. J. Clermont, J. Am. Chem. Soc. 1981, 103, 3127.
62. The pKa values of CF3H and HMDS are comparable and the proton source of the product cannot be specified. HMDS pKa=26 (in THF): R. R. Fraser, T. S. Mansour, S. Savard, J. Org. Chem. 1985, 50, 3232.