Umpolung of Methylenephosphonium Ions in Their Manganese Half-Sandwich Complexes and Application to the Synthesis of Chiral Phosphorus-Containing Ligand Scaffolds†
Corresponding Author
Dr. Dmitry A. Valyaev
Laboratoire de Chimie de Coordination du CNRS (UPR 8241), 205 route de Narbonne, BP 44099, 31077 Toulouse Cedex 4 (France) http://www.lcc-toulouse.fr/lcc/spip.php?article24
Université de Toulouse, UPS, INPT, 31077 Toulouse Cedex 4 (France)
Laboratoire de Chimie de Coordination du CNRS (UPR 8241), 205 route de Narbonne, BP 44099, 31077 Toulouse Cedex 4 (France) http://www.lcc-toulouse.fr/lcc/spip.php?article24Search for more papers by this authorDr. Oleg A. Filippov
A. N. Nesmeyanov Institute of Organoelement Compounds (INEOS), Russian Academy of Sciences, 28 Vavilov Street, GSP-1, B-334, Moscow (Russia)
Search for more papers by this authorCorresponding Author
Dr. Noël Lugan
Laboratoire de Chimie de Coordination du CNRS (UPR 8241), 205 route de Narbonne, BP 44099, 31077 Toulouse Cedex 4 (France) http://www.lcc-toulouse.fr/lcc/spip.php?article24
Université de Toulouse, UPS, INPT, 31077 Toulouse Cedex 4 (France)
Laboratoire de Chimie de Coordination du CNRS (UPR 8241), 205 route de Narbonne, BP 44099, 31077 Toulouse Cedex 4 (France) http://www.lcc-toulouse.fr/lcc/spip.php?article24Search for more papers by this authorDr. Guy Lavigne
Laboratoire de Chimie de Coordination du CNRS (UPR 8241), 205 route de Narbonne, BP 44099, 31077 Toulouse Cedex 4 (France) http://www.lcc-toulouse.fr/lcc/spip.php?article24
Université de Toulouse, UPS, INPT, 31077 Toulouse Cedex 4 (France)
Search for more papers by this authorProf. Dr. Nikolai A. Ustynyuk
A. N. Nesmeyanov Institute of Organoelement Compounds (INEOS), Russian Academy of Sciences, 28 Vavilov Street, GSP-1, B-334, Moscow (Russia)
Search for more papers by this authorCorresponding Author
Dr. Dmitry A. Valyaev
Laboratoire de Chimie de Coordination du CNRS (UPR 8241), 205 route de Narbonne, BP 44099, 31077 Toulouse Cedex 4 (France) http://www.lcc-toulouse.fr/lcc/spip.php?article24
Université de Toulouse, UPS, INPT, 31077 Toulouse Cedex 4 (France)
Laboratoire de Chimie de Coordination du CNRS (UPR 8241), 205 route de Narbonne, BP 44099, 31077 Toulouse Cedex 4 (France) http://www.lcc-toulouse.fr/lcc/spip.php?article24Search for more papers by this authorDr. Oleg A. Filippov
A. N. Nesmeyanov Institute of Organoelement Compounds (INEOS), Russian Academy of Sciences, 28 Vavilov Street, GSP-1, B-334, Moscow (Russia)
Search for more papers by this authorCorresponding Author
Dr. Noël Lugan
Laboratoire de Chimie de Coordination du CNRS (UPR 8241), 205 route de Narbonne, BP 44099, 31077 Toulouse Cedex 4 (France) http://www.lcc-toulouse.fr/lcc/spip.php?article24
Université de Toulouse, UPS, INPT, 31077 Toulouse Cedex 4 (France)
Laboratoire de Chimie de Coordination du CNRS (UPR 8241), 205 route de Narbonne, BP 44099, 31077 Toulouse Cedex 4 (France) http://www.lcc-toulouse.fr/lcc/spip.php?article24Search for more papers by this authorDr. Guy Lavigne
Laboratoire de Chimie de Coordination du CNRS (UPR 8241), 205 route de Narbonne, BP 44099, 31077 Toulouse Cedex 4 (France) http://www.lcc-toulouse.fr/lcc/spip.php?article24
Université de Toulouse, UPS, INPT, 31077 Toulouse Cedex 4 (France)
Search for more papers by this authorProf. Dr. Nikolai A. Ustynyuk
A. N. Nesmeyanov Institute of Organoelement Compounds (INEOS), Russian Academy of Sciences, 28 Vavilov Street, GSP-1, B-334, Moscow (Russia)
Search for more papers by this authorFinancial support from the CNRS and the PICS grant 4873 (CNRS)/09-03-91060 (RFBR) is gratefully acknowledged. O.A.F. is grateful to the Russian Scientific Foundation (grant 14-13-00801) for financial support of DFT calculations. D.A.V. thanks the IDEX-UNITI for a starting grant.
Graphical Abstract
Reactivity trend reversal: Methylenephosphonium salts coordinated to a manganese center were found to exhibit “iminium-like” reactivity towards nucleophiles (see scheme). This unprecedented umpolung enables the instant formation of carbon–heteroatom bonds, highlighted by the synthesis of novel chiral pincer-type phosphine–NHC–phosphine ligands.
Abstract
Half-sandwich manganese methylenephosphonium complexes [Cp(CO)2Mn(η2-R2PC(H)Ph)]BF4 were obtained in high yield through a straightforward reaction sequence involving a classical Fischer-type manganese complex and a secondary phosphine as key starting materials. The addition of various nucleophiles (Nu) to these species took place regioselectively at the double-bonded carbon center of the coordinated methylenephosphonium ligand R2P+C(H)Ph to produce the corresponding chiral phosphine complexes [Cp(CO)2Mn(κ1-R2PC(H)(Ph)Nu)], from which the phosphines were ultimately recovered as free entities upon simple irradiation with visible light. The synthetic potential of this umpolung approach is illustrated herein by the preparation of novel chiral pincer-type phosphine–NHC–phosphine ligand architectures.
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References
- 1
- 1a Iminium Salts in Organic Chemistry, Parts 1 and 2 (Eds.: ), Wiley, New York, 1976;
- 1bE. D. Cox, J. M. Cook, Chem. Rev. 1995, 95, 1797–1842;
- 1cM. Arend, B. Westermann, N. Risch, Angew. Chem. Int. Ed. 1998, 37, 1044–1070;
10.1002/(SICI)1521-3773(19980504)37:8<1044::AID-ANIE1044>3.0.CO;2-E CAS PubMed Web of Science® Google ScholarAngew. Chem. 1998, 110, 1096–1122;
- 1dS. K. Bur, S. F. Martin, Tetrahedron 2001, 57, 3221–3242;
- 1eJ. Royer, M. Bonin, L. Micouin, Chem. Rev. 2004, 104, 2311–2352;
- 1fB. E. Maryanoff, H.-C. Zhang, J. H. Cohen, I. J. Turchi, C. A. Maryanoff, Chem. Rev. 2004, 104, 1431–1628;
- 1gA. Erkkilä, I. Majander, P. M. Pihko, Chem. Rev. 2007, 107, 5416–5470.
- 2For selected reviews, see:
- 2aB. List, Chem. Commun. 2006, 819–824;
- 2bG. Lelais, D. W. C. MacMillan, Aldrichimica Acta 2006, 39, 79–87;
- 2cS. Mukherjee, J. W. Yang, S. Hoffmann, B. List, Chem. Rev. 2007, 107, 5471–5569;
- 2dC. Grondal, M. Jeanty, D. Enders, Nat. Chem. 2010, 2, 167–178;
- 2eM. Nielsen, D. Worgull, T. Zweifel, B. Gschwend, S. Bertelsen, K. A. Jørgensen, Chem. Commun. 2011, 47, 632–649;
- 2fK. L. Jensen, G. Dickmeiss, H. Jiang, L. Albrecht, K. A. Jørgensen, Acc. Chem. Res. 2012, 45, 248–264.
- 3For a review, see:
- 3aH. Grützmacher, C. M. Marchand, Coord. Chem. Rev. 1997, 163, 287–344;
- 3bO. Guerret, G. Bertrand, Acc. Chem. Res. 1997, 30, 486–493;
- 3cR. C. Fischer, P. P. Power, Chem. Rev. 2010, 110, 3877–3923.
- 4
- 4aA. Igau, A. Baceiredo, H. Grützmacher, H. Pritzkow, G. Bertrand, J. Am. Chem. Soc. 1989, 111, 6853–6854;
- 4bH. Grützmacher, H. Pritzkow, Angew. Chem. Int. Ed. Engl. 1991, 30, 709–710; Angew. Chem. 1991, 103, 721–723;
- 4cH. Grützmacher, H. Pritzkow, Angew. Chem. Int. Ed. Engl. 1992, 31, 99–101; Angew. Chem. 1992, 104, 92–94;
- 4dU. Heim, H. Pritzkow, H. Schönberg, H. Grützmacher, J. Chem. Soc. Chem. Commun. 1993, 673–674;
- 4eU. Heim, H. Pritzkow, U. Fleischer, H. Grützmacher, Angew. Chem. Int. Ed. Engl. 1993, 32, 1359–1361; Angew. Chem. 1993, 105, 1400–1402;
- 4fU. Heim, H. Pritzkow, U. Fleischer, H. Grützmacher, M. Sanchez, R. Réau, G. Bertrand, Chem. Eur. J. 1996, 2, 68–74;
- 4gJ. Thomaier, G. Alcaraz, H. Grützmacher, H. Hillebrecht, C. Marchand, U. Heim, J. Organomet. Chem. 1997, 535, 91–97;
- 4hJ. I. Bates, D. P. Gates, J. Am. Chem. Soc. 2006, 128, 15998–15999;
- 4iF. Lavigne, E. Maerten, G. Alcaraz, N. Saffon-Merceron, C. Acosta-Silva, V. Branchadell, A. Baceiredo, J. Am. Chem. Soc. 2010, 132, 8864–8865;
- 4jJ. I. Bates, D. P. Gates, Chem. Eur. J. 2012, 18, 1674–1683;
- 4kY. Hasegawa, G. Kehr, S. Ehrlich, S. Grimme, C. G. Daniliuc, G. Erker, Chem. Sci. 2014, 5, 797–803;
- 4lY. Hasegawa, C. G. Daniliuc, G. Kehr, G. Erker, Angew. Chem. Int. Ed. 2014, 53, 12168–12171; Angew. Chem. 2014, 126, 12364–12367.
- 5
- 5aD. A. Valyaev, N. Lugan, G. Lavigne, N. A. Ustynyuk, Organometallics 2008, 27, 5180–5183;
- 5bD. A. Valyaev, N. Lugan, G. Lavigne, N. A. Ustynyuk, Organometallics 2011, 30, 2318–2332.
- 6The parent cationic tungsten complexes were obtained upon the protonation of η2-phosphinocarbene or oxaphosphirane complexes:
- 6aT. Lehotkay, P. Jaitner, K. Wurst, F. R. Kreissl, J. Organomet. Chem. 1999, 583, 120–125;
- 6bJ. Marinas Pérez, H. Helten, B. Donnadieu, C. A. Reed, R. Streubel, Angew. Chem. Int. Ed. 2010, 49, 2615–2618; Angew. Chem. 2010, 122, 2670–2674.
- 7For selected examples of related neutral phosphinomethanide complexes of Group 4–8 transition metals, see:
- 7aH. H. Karsch, H. F. Klein, H. Schmidbaur, Angew. Chem. 1975, 87, 630–631;
- 7bN. Bresciani, M. Calligaris, P. Delise, G. Nardin, L. Randaccio, J. Am. Chem. Soc. 1974, 96, 5642–5643;
- 7cJ. W. Rathke, E. L. Muetterties, J. Am. Chem. Soc. 1975, 97, 3272–3273;
- 7dH. H. Karsch, H. Schmidbaur, Z. Naturforsch. B 1977, 32, 762–767;
- 7eV. C. Gibson, P. D. Grebenik, M. L. H. Green, J. Chem. Soc. Chem. Commun. 1983, 1101–1102;
- 7fR. G. Bergman, P. F. Seidler, T. T. Wenzel, J. Am. Chem. Soc. 1985, 107, 4358–4362;
- 7gV. C. Gibson, C. E. Graimann, P. M. Hare, M. L. H. Green, J. A. Bandy, P. D. Grebenik, K. Prout, J. Chem. Soc. Dalton Trans. 1985, 2025–2035;
- 7hJ. Gotzig, R. Werner, H. Werner, J. Organomet. Chem. 1985, 290, 99–114;
- 7iH. H. Karsch, B. Deubelly, J. Hofmann, U. Pieper, G. Müller, J. Am. Chem. Soc. 1988, 110, 3654–3656.
- 8D. B. Grotjahn, G. A. Bikzhanova, L. S. B. Collins, T. Concolino, K.-C. Lam, A. L. Rheingold, J. Am. Chem. Soc. 2000, 122, 5222–5223.
- 9For related implicit CO deinsertion processes from ketene ligands, see:
- 9aA. Miyashita, H. Shitara, H. Nohira, Organometallics 1985, 4, 1463–1466;
- 9bA. Savaranamuthu, A. E. Bruce, M. R. M. Bruce, M. C. Fermin, A. S. Hneihen, J. W. Bruno, Organometallics 1992, 11, 2190–2198;
- 9cA. Miyashita, R. Sugai, J. Yamamoto, J. Organomet. Chem. 1992, 428, 239–247;
- 9dY. Ortin, Y. Coppel, N. Lugan, R. Mathieu, M. J. McGlinchey, Chem. Commun. 2001, 2636–2637;
- 9eI. Fernández, M. A. Sierra, M. Gómez-Gallego, M. J. Mancheňo, F. P. Cossío, Chem. Eur. J. 2005, 11, 5988–5996;
- 9fI. Fernández, M. A. Sierra, M. Gómez-Gallego, M. J. Mancheňo, F. P. Cossío, J. Am. Chem. Soc. 2008, 130, 13892–13899;
- 9gI. Fernández, F. P. Cossío, M. A. Sierra, Acc. Chem. Res. 2011, 44, 479–490.
- 10The storage of [5] BF4 in an open vessel for 2 weeks at room temperature resulted in less than 5 % conversion into hydrolysis products on the basis of IR spectroscopic data.
- 11J. Marinas Pérez, C. Albrecht, H. Helten, G. Schnakenburg, R. Streubel, Chem. Commun. 2010, 46, 7244–7246.
- 12CCDC 1045545, 1045546, 1045547, 1045548, and 1045549 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
- 13K. G. Caulton, Coord. Chem. Rev. 1981, 38, 1–43.
- 14C. Barbeau, K. S. Dichmann, L. Ricard, Can. J. Chem. 1973, 51, 3027–3031.
- 15Complex 1 can be prepared in one step in 90 % yield on a 100 mmol scale from [{Mp}(CO)], known as cymantrene, which is produced industrially as an antiknocking fuel additive.
- 16D. A. Valyaev, S. Bastin, K. I. Utegenov, N. Lugan, G. Lavigne, N. A. Ustynyuk, Chem. Eur. J. 2014, 20, 2175–2178.
- 17
- 17aA. A. Danopoulos, N. Tsoureas, S. A. Macgregor, C. Smith, Organometallics 2007, 26, 253–263;
- 17bF. E. Hahn, A. R. Naziruddin, A. Hepp, T. Pape, Organometallics 2010, 29, 5283–5288;
- 17cA. R. Naziruddin, A. Hepp, T. Pape, F. E. Hahn, Organometallics 2011, 30, 5859–5866;
- 17dH. Salem, M. Schmitt, U. Herrlich, E. Kühnel, M. Brill, P. Nägele, A. L. Bogado, F. Rominger, P. Hofmann, Organometallics 2013, 32, 29–46;
- 17eM. Brill, E. Kühnel, C. Scriban, F. Rominger, P. Hofmann, Dalton Trans. 2013, 42, 12861–12864.
- 18Several complexes with similar achiral pincer-type phosphine–perimidinylidene–phosphine ligands were recently reported:
- 18aA. F. Hill, C. M. A. McQueen, Organometallics 2012, 31, 8051–8054;
- 18bA. F. Hill, C. M. A. McQueen, Organometallics 2014, 33, 1909–1912.
- 19
- 19aW. A. Herrmann, M. Elison, J. Fischer, C. Köcher, G. R. J. Artus, Chem. Eur. J. 1996, 2, 772–780;
- 19bV. César, S. Bellemin-Laponnaz, L. H. Gade, Eur. J. Inorg. Chem. 2004, 3436–3444.
