Communication
Organic & Biomolecular Chemistry
Table 3 Copper catalysed P–H insertion into carbene reactionsa
toward establishing a new horizon for controlling reactions via
different catalysts types.
Acknowledgements
We gratefully acknowledge the National Natural Science Foun-
dation of China (21172106, 21074054), the National Science
Fund for Talent Training in Basic Science (No. J1103310), the
National Basic Research Program of China (2010CB923303),
and the Research Fund for the Doctoral Program of Higher
Education of China (20120091110010) for their financial
support.
Notes and references
1 (a) S. Van der Jeught and C. V. Stevens, Chem. Rev., 2009,
109, 2672; (b) C. S. Demmer, N. Krogsgaard-Larsen and
L. Bunch, Chem. Rev., 2011, 111, 7981; (c) L. Coudray and
J. L. Montchamp, Eur. J. Org. Chem., 2008, 3601; (d) The
Chemistry
of
Organophosphorous
Compounds,
ed.
a Reaction conditions: 1 (0.5 mmol), 2 (0.55 mmol), copper (5 mol%,
0.025 mmol), ClCH2CH2Cl (2.0 mL), room temperature, yield of
isolated product.
F. H. Hartley, Wiley, New York, 1996; (e) T. S. Kumar,
S. Y. Zhou, B. V. Joshi, R. Balasubramanian, T. Yang,
B. T. Liang and K. A. Jacobson, J. Med. Chem., 2010, 53,
2562; (f) P. Lassaux, M. Hamel, M. Gulea, H. Delbrck,
P. S. Mercuri, L. Horsfall, D. Dehareng, M. L. Kupper,
J. M. Frre, K. Hoffmann, M. Galleni and C. Bebrone, J. Med.
Chem., 2010, 53, 4862.
2 (a) M. Niu, H. Fu, Y. Jiang and Y. Zhao, Chem. Commun.,
2007, 272; (b) L. B. Han and M. Tanaka, J. Am. Chem. Soc.,
1996, 118, 1571; (c) L. B. Han, Y. Ono and S. Shimada, J.
Am. Chem. Soc., 2008, 130, 2752; (d) Y. Gao, G. Wang,
L. Chen, P. Xu, Y. Zhao, Y. Zhou and L. B. Han, J. Am.
Chem. Soc., 2009, 131, 7956; (e) L. B. Han and T. Don Tilley,
J. Am. Chem. Soc., 2006, 128, 13698; (f) J. Hu, N. Zhao,
B. Yang, G. Wang, L. N. Guo, Y. M. Liang and S. D. Yang,
Chem.–Eur. J., 2011, 17, 5516.
3 (a) T. Ye and M. A. McKervey, Chem. Rev., 1994, 94, 1091;
(b) A. Padwa and D. J. Austin, Angew. Chem., Int. Ed. Engl.,
1994, 33, 1797; (c) A. Padwa and M. D. Weingarten, Chem.
Rev., 1996, 96, 223; (d) M. P. Doyle, M. A. McKervey and
T. Ye, in Modern Catalytic Methods for Organic Synthesis
with Diazo Compounds, Wiley, New York, 1998;
(e) D. M. Hodgson, F. Y. T. M. Pierard and P. A. Stupple,
Chem. Soc. Rev., 2001, 30, 50; (f) H. M. L. Davies and
E. G. Antoulinakis, J. Organomet. Chem., 2001, 617/618, 47;
(g) H. M. L. Davies and R. E. J. Beckwith, Chem. Rev., 2003,
103, 2861; (h) G. S. Singh and L. K. Mdee, Curr. Org. Chem.,
2003, 7, 1821; (i) G. S. Singh, Curr. Org. Synth., 2005, 2, 377;
( j) M. M. DíazRequejo and P. J. Pérez, J. Organomet. Chem.,
2005, 690, 5441; (k) A. G. H. Wee, Curr. Org. Synth., 2006, 3,
499; (l) Metal Carbenes in Organic Synthesis, ed.
F. Z. Dorwald, Wiley-VCH, 2007; (m) Y. Zhang and
J. B. Wang, Chem. Commun., 2009, 5350; (n) X. Zhao,
Y. Zhang and J. B. Wang, Chem. Commun., 2012, 48, 10162.
corresponding products in moderate to high yields (Table 2,
3d–3k). Meanwhile, some other phosphonates and the ali-
phatic α-diazoester were also applied under the standard con-
ditions; they furnished the product smoothly with good results
(Table 2, 3l–3n). Notably, diphenylphosphine oxide was also
good substrate for the coupling reactions, and gave the
product 3o with high yield.
Then, the scope of the copper catalysed P–H insertion into
the carbene formed from α-diazoesters in situ under the
optimal reaction conditions (entry 7, Table 3) was also investi-
gated. The substrate scope of the C–P bond formation reaction
is broad, different substituted groups on the α-diazoesters
could be well tolerated and provide the desired products 4a–i
in excellent yields (85–98%). In addition, the aliphatic α-dia-
zoester was also good substrate for this protocol and afforded
the corresponding product 4j. Intriguingly, when diphenylpho-
sphine oxide was used, the desired products 4k–4l were effec-
tively obtained. However, the reaction did not work with
aliphatic phosphonates under the standard reaction con-
ditions, no products were detected, which may due to its low
activity.
In summary, we have uncovered a switchable catalytic reac-
tion between phosphorus compounds and α-diazoesters by
using an organomolecule (DBU) and copper as catalysts. Selec-
tive N–P bond formation was achieved when DBU was applied
as organocatalyst, while C–P bond was formed with the copper
catalyst. The process demonstrated the diverse reactivity of
α-diazoesters that could be controlled by organomolecule and
metal. The new methodology offered facile access to various
phosphorus compounds and provided an excellent option
3614 | Org. Biomol. Chem., 2013, 11, 3612–3615
This journal is © The Royal Society of Chemistry 2013