CREATED USING THE RSC COMMUNICATION TEMPLATE (VER. 3.1) - SEE WWW.RSC.ORG/ELECTRONICFILES FOR DETAILS
Page 3 of 3
Dalton Transactions
DOI: 10.1039/C5DT01281C
ARTICLE TYPE
45
50
55
60
65
70
Webster, M. C. White and G. T. Whiteker, Organometallics, 2014,
33, 1505-1527.
5. R. Engel and J. I. Cohen, Synthesis of Carbon–Phosphorus Bonds,
CRC Press: Boca Raton, 2nd edn., 2004.
6. P. G. M. Wuts and T. W. Greene, Greene’s Protective Groups in
Organic Synthesis, Wiley, Hoboken, 4th edn., 2007.
7. A. Michaelis, Chem. Ber., 1879, 12, 1009-1009.
In summary, we have demonstrated that in the presence of
AlCl3 or after treatment with AgOSO2CF3, tungsten-coordinated
chlorophosphines undergo facile and regioselective electrophilic
substitution reactions with various unsaturated substrates. These
reactions can be applied sequentially in a controlled fashion to
dichloro phosphines and aminodichlorophosphines. The two
chloride abstractors AlCl3 and AgOSO2CF3 are complementary,
and most potential substrates are compatible with one or the
other. As a result, functional group compatibility is wide. Further,
5
8. J. A. Miles, M. T. Beeny and K. W. Ratts, J. Org. Chem., 1975, 40,
343-347.
9. (a) A. H. Cowley, R. A. Kemp and J. C. Wilburn, Inorg. Chem.,
1981, 20, 4289-4293; (b) H. Nakazawa, Y. Yamaguchi, K.
Kawamura and K. Miyoshi, Organometallics, 1997, 16, 4626-4635;
(c) K. Jörg, W. Malisch, W. Reich, A. Meyer and U. Schubert,
Angew. Chem., Int. Ed., 1986, 25, 92-93; (d) W. Malisch, U.-A.
Hirth, K. Grün, M. Schmeusser, O. Fey and U. Weis, Angew. Chem.,
Int. Ed., 1995, 34, 2500-2502; (e) Y. Yamaguchi, H. Nakazawa, M.
Kishishita and K. Miyoshi, Organometallics, 1996, 15, 4383-4388;
(f) R. W. Parry and J. M. Higashi, Fluorine Chem., 1995, 71, 221-
222.
10. (a) K. Kawamura, H. Nakazawa and K. Miyoshi, Organometallics,
1999, 18, 4785-4794; (b) H. Nakazawa, M. Ohta, K. Miyoshi and H.
Yoneda, Organometallics, 1989, 8, 638-644; (c) H. Nakazawa, Y.
Yamaguchi, T. Mizuta, S. Ichimura and K Miyoshi, Organometallics,
1995, 14, 4635-4643.
Fe1
C17
W1
P1
C6
C9
11. (a) A. Jayaraman and B. T. Sterenberg, Organometallics, 2013, 32,
745-747; (b) A. Jayaraman and B. T. Sterenberg, Organometallics,
2014, 33, 522-530.
C7
N1
12. (a) E. Ocando, S. Majid, J. Pierre Majoral, A. Baceiredo and G.
Bertrand, Polyhedron, 1985, 4, 1667-1668; (b) C. Zeiher, W. Hiller
and I.-P. Lorenz, Chem. Ber., 1985, 118, 3127-3134.
C8
10
75 13. C. Baillie, L. Zhang and J. Xiao, J. Org. Chem., 2004, 69, 7779-
Figure 1. ORTEP diagram showing the molecular structure of 16.
Thermal ellipsoids are shown at the 50% probability level, and H atoms
have been omitted.
7782.
14. F. Ho, R. Ganguly and F. Mathey, Eur. J. Inorg. Chem., 2014, 2014,
4726-4729.
15. A. Marinetti, S. Bauer, L. Ricard and F. Mathey, Organometallics,
these reactions all occur at room temperature or lower. A
80
85
90
1990, 9, 793-798.
15 systematic investigation on the reactivity of these metal-
coordinated chlorophosphines with other functionalized aromatic
substrates, and other organic substrates such as alkenes, alkynes,
and ketones is currently underway. Because reactions are rapid
and high-yielding, and can be applied to a wide range of organic
20 substrates, they are potentially valuable tools for P–C bond
formation and phosphine ligand synthesis. We are also now
extending this methodology to lower cost metals like iron, and
catalytically active metals like palladium.
16. H. Meinert, H. Vogt, B. Pahnke and G. Schulenburg, Z. Chem., 1980,
20, 110-111.
17. (a) M. B. Abrams, B. L. Scott and R. T. Baker, Organometallics,
2000, 19, 4944-4956; (b) R. A. Rajagopalan, A. Jayaraman and B. T.
Sterenberg, J. Organomet. Chem., 2014, 761, 84-92; (c) A. H.
Cowley and R. A. Kemp, Chem. Rev., 1985, 85, 367-382; (d) M. T.
Nguyen, A. Van Keer and L. G. Vanquickenborne, J. Org. Chem.,
1996, 61, 7077-7084.
18. (a) F. Mercier and F. Mathey, J. Chem. Soc., Chem. Commun., 1984,
782-783. (b) M. L. G. Borst, R. E. Bulo, D. J. Gibney, Y. Alem, F. J.
J. de Kanter, A. W. Ehlers, M. Schakel, M. Lutz, A. L. Spek and K.
Lammertsma, J. Am. Chem. Soc., 2005, 127, 16985-16999.
This work was financially supported by the University of
25 Regina. We thank Bob McDonald and Mike Ferguson
(University of Alberta) for X-ray data collection.
Notes and references
Department of Chemistry and Biochemistry, University of Regina, 3737
Wascana Parkway, Regina, Saskatchewan S4S 0A2, Canada. Tel:
30 1(306)585-4106; E-mail: brian.sterenberg@uregina.ca
† Electronic Supplementary Information (ESI) available: Experimental
details and compound characterization data. A CIF file containing
crystallographic data for 16. See DOI: 10.1039/b000000x/
35
1. R. Bates, Organic Synthesis Using Transition Metals, Wiley:
Chichester,1st edn., 2012.
2. J. L. Methot and W. R. Roush, Adv. Synth. Catal., 2004, 346, 1035-
1050.
40 3. L. D. Quin, A Guide to Organophosphorus Chemistry, Wiley, New
York, 1st edn., 2000.
4. J. A. Gladysz, R. B. Bedford, M. Fujita, F. P. Gabbaï, K. I. Goldberg,
P. L. Holland, J. L. Kiplinger, M. J. Krische, J. Louie, C. C. Lu, J. R.
Norton, M. A. Petrukhina, T. Ren, S. S. Stahl, T. D. Tilley, C. E.
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 3