Alkali Metal Carbenoids: A Case of Higher Stability of the Heavier Congeners

Angewandte Chemie - International Edition

Volumn 55, Issue 27, 2016, Pages 7712-7716

  Molitor, Sebastian ^a   Gessner, Viktoria H ^a  

^a UNIVERSITY OF WÜRZBURG   (Germany)

Author keywords

alkali metals; carbanions; carbenoids; lithium; structure activity relationships

Indexed keywords

ALKALI METALS; CROWN ETHERS; LITHIUM;

CARBANIONS; CARBENE TRANSFER; CARBENOIDS; LITHIUM SYSTEMS; PERIODIC TABLE; PRODUCT MIXTURE; SIMPLE SUBSTITUTION; STRUCTURE ELUCIDATION;

ALKALI METAL COMPOUNDS;

EID: 84976551830     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201601356     Document Type: Article

References (88)

1. P. P. Power, Nature 2010, 463, 171;
2. A. L. Kenward, W. E. Piers, Angew. Chem. Int. Ed. 2008, 47, 38;
3. Angew. Chem. 2008, 120, 38.
4. G. D. Frey, V. Lavallo, B. Donnadieu, W. W. Schoeller, G. Bertrand, Science 2007, 316, 439;
5. V. Lavallo, Y. Canac, B. Donnadieu, W. W. Schoeller, G. Bertrand, Angew. Chem. Int. Ed. 2006, 45, 3488;
6. Angew. Chem. 2006, 118, 3568;
7. J. D. Masuda, W. W. Schoeller, B. Donnadieu, G. Bertrand, Angew. Chem. Int. Ed. 2007, 46, 7052;
8. Angew. Chem. 2007, 119, 7182;
9. T. W. Hudnall, J. P. Moerdyk, C. W. Bielawski, Chem. Commun. 2010, 46, 4288.
10. D. W. Stephan, G. Erker, Angew. Chem. Int. Ed. 2015, 54, 6400;
11. Angew. Chem. 2015, 127, 6498;
12. D. W. Stephan, G. Erker, Angew. Chem. Int. Ed. 2010, 49, 46;
13. Angew. Chem. 2010, 122, 50;
14. G. C. Welch, R. R. S. Juan, J. D. Masuda, D. W. Stephan, Science 2006, 314, 1124.
15. G. Boche, J. C. W. Lohrenz, Chem. Rev. 2001, 101, 697;
16. G. Köbrich, Angew. Chem. Int. Ed. Engl. 1972, 11, 473;
17. Angew. Chem. 1972, 84, 557;
18. V. Capriati, S. Florio, Chem. Eur. J. 2010, 16, 4152.
19. D. M. Hodgson, S. Salik, D. J. Fox, J. Org. Chem. 2010, 75, 2157;
20. V. Capriati, S. Florio, R. Luisi, M. T. Rochetti, J. Org. Chem. 2002, 67, 759;
21. H. Lebel, J.-F. Marcoux, C. Molinaro, A. B. Charette, Chem. Rev. 2003, 103, 977;
22. S. Taillemaud, N. Diercxsens, A. Gagnon, A. B. Charette, Angew. Chem. Int. Ed. 2015, 54, 14108;
23. Angew. Chem. 2015, 127, 14314;
24. R. Mansueto, V. Mallardo, F. M. Perna, A. Salomone, V. Capriati, Chem. Commun. 2013, 49, 10160.
25. M. Pasco, N. Gilboa, T. Mejuch, I. Marek, Organometallics 2013, 32, 942;
26. V. Pace, L. Castoldi, W. Holzer, Chem. Commun. 2013, 49, 8383;
27. J. P. Varghese, I. Zouev, L. Aufauvre, P. Knochel, I. Marek, Eur. J. Org. Chem. 2002, 4151;
28. V. Pace, A. Pelosi, D. Antermite, O. Rosati, M. Curini, W. Holzer, Chem. Commun. 2016, 52, 2639.
29. J. L. Stymiest, V. Bagutski, R. M. French, V. K. Aggarwal, Nature 2008, 456, 778;
30. S. Roesner, D. J. Blair, V. K. Aggarwal, Chem. Sci. 2015, 6, 3718;
31. R. Rasappan, V. K. Aggarwal, Nat. Chem. 2014, 6, 810.
32. G. Boche, M. Marsch, A. Müller, K. Harms, Angew. Chem. Int. Ed. Engl. 1993, 32, 1032.
33. T. Cantat, X. Jacques, L. Ricard, X. F. Le Goff, N. Mézailles, P. Le Floch, Angew. Chem. Int. Ed. 2007, 46, 5947;
34. Angew. Chem. 2007, 119, 6051.
35. H. Heuclin, S. Y.-F. Ho, X. F. Le Goff, C.-W. So, N. Mézailles, J. Am. Chem. Soc. 2013, 135, 8774;
36. S. Molitor, V. H. Gessner, Chem. Eur. J. 2013, 19, 11858;
37. S. Molitor, V. H. Gessner, Synlett 2015, 26, 861;
38. S. Molitor, V. H. Gessner, J. Am. Chem. Soc. 2014, 136, 15517.
39. S. Y.-F. Ho, C.-W. So, N. Saffon-Merceron, N. Mézailles, Chem. Commun. 2015, 51, 2107.
40. K.-S. Feichtner, V. H. Gessner, Dalton Trans. 2014, 43, 14399;
41. J. Becker, V. H. Gessner, Organometallics 2014, 33, 1310;
42. S. Molitor, K.-S. Feichtner, C. Kupper, V. H. Gessner, Chem. Eur. J. 2014, 20, 10752;
43. J. Becker, V. H. Gessner, Dalton Trans. 2014, 43, 4320.
44. G. Köbrich, Angew. Chem. Int. Ed. Engl. 1967, 6, 41;
45. Angew. Chem. 1967, 79, 15;
46. G. Ludwig, D. Ströhl, H. Schmidt, D. Steinborn, Inorg. Chim. Acta 2015, 429, 30;
47. T. Rüffer, C. Bruhn, A. H. Maulitz, D. Ströhl, D. Steinborn, Organometallics 2000, 19, 2829;
48. B. Waerder, S. Steinhauer, B. Neumann, H.-G. Stammler, A. Mix, Y. V. Vishnevskiy, B. Hoge, N. W. Mitzel, Angew. Chem. Int. Ed. 2014, 53, 11640;
49. Angew. Chem. 2014, 126, 11824;
50. A. Salomone, F. M. Perna, A. Falcicchio, S. O. Nilsson Lill, A. Moliterni, R. Michel, S. Florio, D. Stalke, V. Capriati, Chem. Sci. 2014, 5, 528;
51. J. Huang, P. O'Brien, Chem. Commun. 2005, 5696;
52. V. Capriati, S. Florio, R. Luisi, F. M. Perna, A. Spina, J. Org. Chem. 2008, 73, 9552.
53. P. von R. Schleyer, T. Clark, A. J. Kos, G. W. Spitznagel, C. Rohde, D. Arad, K. N. Houk, N. G. Rondan, J. Am. Chem. Soc. 1984, 106, 6467.
54. B. Martel, J. M. Hiriart, Tetrahedron Lett. 1971, 12, 2737;
55. A. Oku, T. Harada, Y. Homoto, M. Iwamoto, J. Chem. Soc. Chem. Commun. 1988, 1490.
56. M. Schlosser, Angew. Chem. 1964, 76, 124;
57. D. Seyferth, Organometallics 2006, 25, 2;
58. D. Seyferth, Organometallics 2009, 28, 2;
59. L. Orzechowski, G. Jansen, S. Harder, Angew. Chem. Int. Ed. 2009, 48, 3825;
60. Angew. Chem. 2009, 121, 3883.
61. N. I. Pakuro, A. A. Arest-Yakubovich, L. V. Shcheglova, P. V. Petrovsky, L. A. Cheklaeva, Russ. Chem. Bull. 1996, 45, 838;
62. C. Schade, W. Bauer, P. von R. Schleyer, J. Organomet. Chem. 1985, 295, c25;
63. R. Pi, W. Bauer, B. Brix, C. Schade, P. von R. Schleyer, J. Organomet. Chem. 1986, 306, C1;
64. E. C. Border, M. Koutsaplis, P. C. Andrews, Organometallics 2016, 35, 303.
65. A. Müller, M. Marsch, K. Harms, J. C. W. Lohrenz, G. Boche, Angew. Chem. Int. Ed. Engl. 1996, 35, 1518;
66. Angew. Chem. 1996, 108, 1639;
67. D. Seebach, H. Siegel, K. Müllen, K. Hiltbrunner, Angew. Chem. Int. Ed. Engl. 1979, 18, 784;
68. Angew. Chem. 1979, 91, 844;
69. H. Siegel, K. Hiltbrunner, D. Seebach, Angew. Chem. Int. Ed. Engl. 1979, 18, 785;
70. Angew. Chem. 1979, 91, 845.
71. The high-field shift of C1 in 1-Li suggests a lower carbenoid character (Ref. [4a,c]). However, 1-Li is the most reactive system in the series 1-M which indicates facile LiCl formation. NMR shifts are also influenced by several factors, which may cause the unexpected high-field shift in 1-Li.
72. S. Molitor, C. Schwarz, V. H. Gessner, Organometallics 2016, 35, 159.
73. C. Wills, K. Izod, J. Young, W. Clegg, R. W. Harrington, Dalton Trans. 2009, 6159;
74. D. R. Armstrong, M. G. Davidson, D. Garcia-Vivo, A. R. Kennedy, R. E. Mulvey, S. D. Robertson, Inorg. Chem. 2013, 52, 12023;
75. M. G. Davidson, D. Garcia-Vivo, A. R. Kennedy, R. E. Mulvey, S. D. Robertson, Chem. Eur. J. 2011, 17, 3364;
76. P. C. Andrews, C. L. Raston, B. A. Roberts, B. W. Skelton, A. H. White, J. Organomet. Chem. 2006, 691, 3325.
77. PC coupling constant for C1 suggest no strong C1−M interaction in solution.
78. T. Clark, P. von R. Schleyer, J. Am. Chem. Soc. 1979, 101, 7747;
79. T. Clark, P. von R. Schleyer, J. Chem. Soc. Chem. Commun. 1979, 883;
80. A. R. Kennedy, J. Klett, R. E. Mulvey, D. S. Wright, Science 2009, 326, 706.
81. G. Boche, A. Opel, M. Marsch, K. Harms, F. Haller, J. C. W. Lohrenz, C. Thümmler, W. Koch, Chem. Ber. 1992, 125, 2265;
82. G. Ludwig, T. Rüffer, A. Hoppe, T. Walther, H. Lang, S. G. Ebbinghaus, D. Steinborn, Dalton Trans. 2015, 44, 5323.
83. S. Henkel, P. Costa, L. Klute, P. Sokkar, M. Fernandez-Oliva, W. Thiel, E. Sanchez-Garcia, W. Sander, J. Am. Chem. Soc. 2016, 138, 1689;
84. A. R. Kennedy, R. E. Mulvey, S. D. Robertson, Dalton Trans. 2010, 39, 9091.
85. The decomposition reactions of 1-Na and 1-Li to 2 and MCl have similar reaction enthalpies and Gibbs energies, thus suggesting that the different stabilities are due to kinetic effects (see the Supporting Information for details).
86. E. Poverenov, D. Milstein, Chem. Commun. 2007, 3189;
87. See Ref. [12 d].
88. V. H. Gessner, Organometallics 2011, 30, 4228.