Bis(difluoromethyl)trimethylsilicate Anion: A Key Intermediate in Nucleophilic Difluoromethylation of Enolizable Ketones with Me3SiCF2H

Angewandte Chemie - International Edition

Volumn 55, Issue 41, 2016, Pages 12632-12636

  Chen, Dingben ^a,b   Ni, Chuanfa ^a   Zhao, Yanchuan ^a   Cai, Xian ^a   Li, Xinjin ^a   Xiao, Pan ^a   Hu, Jinbo ^a  

^a SHANGHAI INSTITUTE OF ORGANIC CHEMISTRY   (China)

^b TAIZHOU UNIVERSITY   (China)

Author keywords

fluorine; ketones; reaction mechanisms; reactive intermediates; silicates

Indexed keywords

CATALYSIS; CESIUM COMPOUNDS; CROWN ETHERS; FLUORINE; KETONES; SILICATES; SILICON;

18-CROWN-6; ALKALI METAL SALTS; CATALYTIC REACTIONS; INITIATION SYSTEM; REACTION MECHANISM; REACTIVE INTERMEDIATE; SILICATE ANIONS;

REACTION INTERMEDIATES;

EID: 84992204734     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201605280     Document Type: Article

References (65)

1. Selected reviews:
2. H. Sakurai, Synlett 1989, 1;
3. C. Chuit, R. J. P. Corriu, C. Reye, J. C. Young, Chem. Rev. 1993, 93, 1371;
4. R. R. Holmes, Chem. Rev. 1996, 96, 927;
5. J. Hermanns, B. Schmidt, J. Chem. Soc. Perkin Trans. 1 1999, 81;
6. K. Uneyama, J. Fluorine Chem. 2007, 128, 1087.
7. E. P. A. Couzijn, D. W. F. van den Engel, J. C. Slootweg, F. J. J. de Kanter, A. W. Ehlers, M. Schakel, K. Lammertsma, J. Am. Chem. Soc. 2009, 131, 3741, and references therein;
8. E. P. A. Couzijn, J. C. Slootweg, A. W. Ehlers, K. Lammertsma, Z. Anorg. Allg. Chem. 2009, 635, 1273, and references therein.
9. S. A. Sullivan, C. H. DePuy, R. Damrauer, J. Am. Chem. Soc. 1981, 103, 480;
10. D. A. Dixon, W. R. Hertler, D. B. Chase, W. B. Farnham, F. Davidson, Inorg. Chem. 1988, 27, 4012;
11. I. A. H. J. F. de Keijzer, F. J. J. de Kanter, M. Schakel, R. F. Schmitz, G. W. Klumpp, Angew. Chem. Int. Ed. Engl. 1996, 35, 1127;
12. Angew. Chem. 1996, 108, 1183;
13. A. H. J. F. de Keijzer, F. J. J. de Kanter, M. Schakel, V. P. Osinga, G. W. Klumpp, J. Organomet. Chem. 1997, 548, 29;
14. D. Ballweg, Y. Liu, I. A. Guzei, R. West, Silicon Chem. 2002, 1, 55;
15. S. Deerenberg, M. Schakel, A. H. J. F. de Keijzer, M. Kranenburg, M. Lutz, A. L. Spek, K. Lammertsma, Chem. Commun. 2002, 348;
16. E. P. A. Couzijn, M. Schakel, F. J. J. de Kanter, A. W. Ehlers, M. Lutz, A. L. Spek, K. Lammertsma, Angew. Chem. Int. Ed. 2004, 43, 3440;
17. Angew. Chem. 2004, 116, 3522;
18. E. P. A. Couzijn, A. W. Ehlers, M. Schakel, K. Lammertsma, J. Am. Chem. Soc. 2006, 128, 13634.
19. M. Ishikawa, K. Nishimura, H. Sugisawa, M. Kumada, J. Organomet. Chem. 1981, 218, C21;
20. N. Tokitoh, T. Matsumoto, H. Suzuki, R. Okazaki, Tetrahedron Lett. 1991, 32, 2049;
21. Z. Wang, H. Fang, Z. Xi, Tetrahedron Lett. 2005, 46, 499;
22. L. Bonnafoux, R. Scopelliti, F. R. Leroux, F. Colobert, Tetrahedron Lett. 2007, 48, 8768;
23. P. Zheng, Z. Cai, A. Garimallaprabhakaran, P. Rooshenas, P. R. Schreiner, M. Harmata, Eur. J. Org. Chem. 2011, 5255;
24. M. Onoe, T. Morioka, M. Tobisu, N. Chatani, Chem. Lett. 2013, 42, 238, and references therein.
25. N. Maggiarosa, W. Tyrra, D. Naumann, N. V. Kirij, Y. L. Yagupolskii, Angew. Chem. Int. Ed. 1999, 38, 2252;
26. Angew. Chem. 1999, 111, 2392;
27. A. Kolomeitsev, V. Movchun, E. Rusanov, G. Bissky, E. Lork, G.-V. Roschenthaler, P. Kirsch, Chem. Commun. 1999, 1107;
28. G. K. S. Prakash, F. Wang, Z. Zhang, R. Haiges, M. Rahm, K. O. Christe, T. Mathew, G. A. Olah, Angew. Chem. Int. Ed. 2014, 53, 11575;
29. Angew. Chem. 2014, 126, 11759.
30. S. Steinhauer, J. Bader, H.-G. Stammler, N. Ignat'ev, B. Hoge, Angew. Chem. Int. Ed. 2014, 53, 5206;
31. Angew. Chem. 2014, 126, 5307;
32. W. Tyrra, D. Naumann, N. V. Kirij, A. A. Kolomeitsev, Y. L. Yagupolskii, J. Chem. Soc. Dalton Trans. 1999, 657.
33. Difluoromethylation of carbonyl compounds and imines:
34. T. Hagiwara, T. Fuchikami, Synlett 1995, 717;
35. Y. Zhao, W. Huang, J. Zheng, J. Hu, Org. Lett. 2011, 13, 5342;
36. A. A. Tyutyunov, V. E. Boyko, S. M. Igoumnov, Fluorine Notes 2011, 5(78), http://notes.fluorine1.ru/public/2011/5 2011/letters/letter4.html;
37. G. Du, Y. Wang, C. Gu, B. Dai, L. He, RSC Adv. 2015, 5, 35421;
38. E. Obijalska, G. Utecht, M. K. Kowalski, G. Mlostoń, M. Rachwalski, Tetrahedron Lett. 2015, 56, 4701;
39. O. M. Michurin, D. S. Radchenko, I. V. Komarov, Tetrahedron 2016, 72, 1351.
40. Difluoromethylation of (hetero)arenes:
41. P. S. Fier, J. F. Hartwig, J. Am. Chem. Soc. 2012, 134, 5524;
42. Y. Gu, X. Leng, Q. Shen, Nat. Commun. 2014, 5, 5405;
43. X.-L. Jiang, Z.-H. Chen, X.-H. Xu, F.-L. Qing, Org. Chem. Front. 2014, 1, 774;
44. C. Matheis, K. Jouvin, L. J. Goossen, Org. Lett. 2014, 16, 5984;
45. D. E. Stephens, G. Chavez, M. Valdes, M. Dovalina, H. D. Arman, O. V. Larionov, Org. Biomol. Chem. 2014, 12, 6190;
46. M. Nagase, Y. Kuninobu, M. Kanai, J. Am. Chem. Soc. 2016, 138, 6103;
47. X. Wang, E. Tokunaga, N. ShibataSOR-CHEM.AD, ScienceOpen Research 2014, DOI: 10.14293/S2199-1006.1.1QVW.v2.
48. Difluoromethylation of heteroatoms:
49. B. Bayarmagnai, C. Matheis, K. Jouvin, L. J. Goossen, Angew. Chem. Int. Ed. 2015, 54, 5753;
50. Angew. Chem. 2015, 127, 5845;
51. K. Jouvin, C. Matheis, L. J. Goossen, Chem. Eur. J. 2015, 21, 14324;
52. J.-B. Han, H.-L. Qin, S.-H. Ye, L. Zhu, C.-P. Zhang, J. Org. Chem. 2016, 81, 2506;
53. J. L. Howard, C. Schotten, S. T. Alston, D. L. Browne, Chem. Commun. 2016, 52, 8448.
54. K. Uneyama, Organofluorine Chemistry, Blackwell, Oxford, 2006.
55. G. K. S. Prakash, A. K. Yudin, Chem. Rev. 1997, 97, 757;
56. X. Liu, C. Xu, M. Wang, Q. Liu, Chem. Rev. 2015, 115, 683.
57. G. W. Gokel, W. M. Leevy, M. E. Weber, Chem. Rev. 2004, 104, 2723.
58. W. R. Dolbier, Jr., Guide to Fluorine NMR for Organic Chemists, Wiley, Hoboken, 2009, pp. 118–119.
59. 2H and tBuONa/18-crown-6, see the Supporting Information.
60. 29Si NMR signal of lithium 2,2′-biphenyldiyltrimethylsilicate appears at δ=−116.9 ppm. See Ref. [3c].
61. + with 18-crown-6, see:
62. M. D. Brown, J. M. Dyke, F. Ferrante, W. Levason, J. S. Ogden, M. Webster, Chem. Eur. J. 2006, 12, 2620;
63. T. Arliguie, M. Fourmigué, M. Ephritikhine, Organometallics 2001, 20, 282.
64. 2H (see Ref. [7c]).
65. S. D. Kuduk, N. J. Liverton, J. W. Skudlarek, WO Patent Appl. 176142, 2014.