10.1002/anie.201707102
Angewandte Chemie International Edition
COMMUNICATION
Yan, P. Xu, Y. Gao, Y. Zhao, J. Org. Chem. 2014, 79, 8118; l) W. Chen,
D. Ma, G. Hu, Z. Hong, Y. Gao, Y. Zhao, Synth. Commun. 2016, 46,
1175; Decarbonylative methods: m) R. Yu, X. Chen, S. F. Martin, Z.
Wang, Org. Lett. 2017, 19, 1808; n) see, Ref. 38b; Coupling of nitriles:
o) J. S. Zhang, T. Chen, J. Yang, L. B. Han, Chem. Commun. 2015, 51,
7540; p) M. Sun, Y. S. Zang, L. K. Hou, X. X. Chen, W. Sun, S. D. Yang,
Eur. J. Org. Chem. 2014, 6796; q) M. Sun, H. Y. Zhang, Q. Han, K.
Yang, S. D. Yang, Chem. Eur. J. 2011, 17, 9566.
In summary, we have developed the first deamidative
phosphorylation of amides by palladium and nickel catalysis.
The reaction constitutes the first example of a transition-metal-
catalyzed generation of C–P bonds from amides. This new
process provides an alternative to the classic Hirao reaction and
uses carboxylic acid derived electrophiles. This versatile method
tolerates a wide range of functional groups and accommodates
cyclic and acyclic N-activating groups. Mechanistic studies have
provided support for the oxidative addition/transmetallation
pathway, in which transmetallation proceeds prior to
decarbonylation under both Pd and Ni catalytic conditions.
Considering the ubiquity of organophosphorus compounds in
modern organic synthesis, we expect that this Pd and Ni-
catalyzed C–P bond forming method will be of general interest.
[8]
[9]
a) K. S. Petrakis, T. L. Nagabhushan, J. Am. Chem. Soc. 1987, 109,
2831; b) D. A. Holt, J. M. Erb, Tetrahedron Lett.1989, 30, 5393; c) W. C.
Fu, C. M. So, F. Y. Kwong, Org. Lett.2015, 17, 5906.
R. Berrino, S. Cacchi, G. Fabrizi, A. Goggiamani, P Stabile, Org.
Biomol. Chem. 2010, 8, 4815.
[10] M. Andaloussi, J. Lindh, J. Sävmarker, P. J. R. Sjöberg, M. Larhed,
Chem. Eur. J. 2009, 15, 13069.
[11] H. Luo, H. Liu, X. Chen, K. Wang, X. Luo, K. Wang, Chem. Commun.
2017, 53, 956.
[12] T. Wang, S. Sang, L. Liu, H. Qiao, Y. Gao, Y. Zhao, J. Org. Chem.
2014, 79, 608.
Acknowledgements
[13] J. Yang, T. Chen, L. B. Han, J. Am. Chem. Soc. 2015, 137, 1782.
[14] J. Yang, J. Xiao, T. Chen, S. F. Yin, L. B. Han, Chem. Commun. 2016,
52, 12233.
We thank Rutgers University for financial support. The 500 MHz
spectrometer used in this study was supported by the NSF-MRI
grant (CHE-1229030).
[15] a) Y. L. Zhao, G. J. Wu, Y. Li, L. X. Gao, F. S. Han, Chem. Eur. J. 2012,
18, 9622; b) C. Shen, G. Yang, W. Zhang, Org. Biomol. Chem. 2012,
10, 3500.
[16] a) D. Gelman, L. Jiang, S. L. Buchwald, Org. Lett. 2003, 5, 2315; b) H.
Rao, Y. Jin, H. Fu, Y. Jiang, Y. Zhao, Chem. Eur. J. 2006, 12, 3636.
[17] A. K. Bhattachary, G. Thyarajan, Chem. Rev.1981, 81, 415.
[18] For an excellent perspective, see: J. L. Montchamp, Acc. Chem. Res.
2014, 47, 77.
Keywords: amides • phosphonates • cross-coupling • N–C
activation • carboxylic acids
[1]
a) G. Nemeth, Z. Graff, A. Sipos, Z. Varga, R. Szekely, M. Sebestyen,
Z. Jaszay, S. Beni, Z. Nemes, J. L. Pirat, J. N. Volle, D. Virieux, A.
Gyuris, K. Kelemenics, E. Ay, J. Minarovits, S. Szathamary, G. Keri, L.
Orfi, J. Med. Chem. 2014, 57, 3939; b) W. Jiang, G. Allan, J. J.
Fiordeliso, O. Linton, P. Tannenbaum, J. Xu, P. Zhu, J. Gunnet, K.
Demarest, S. Lundeen, Z. Sui, Bioorg. Med. Chem. 2006, 14, 6726; c)
M. D. Erion, P. D. van Poelje, Q. Dang, S. R. Kasibhatla, S. C. Potter,
M. R. Reddy, K. R. Reddy, T. Jiang, W.N. Lipscomb, Proc. Natl. Sci. U.
S. A. 2005, 102, 7970; d) P. Lassaux, M. Hamel, M. Gulea, H. Delbrück,
P. S. Mercuri, L. Horsfall, D. Dehareng, M. Kupper, J. M. Frere, K.
Hoffmann, M. Galeni, C. Bebrone, J. Med. Chem. 2010, 53, 4862.
a) C. Queffelec, M. Petit, P. Janvier, D. A. Knight, B. Bujoli, Chem. Rev.
2012, 112, 3777; b) H. Onouchi, T. Miyagawa, A. Furuko, K. Maeda, E.
Yashima, J. Am. Chem. Soc. 2005, 127, 2960.
[19] a) C. G. Feng, M. Ye, K. J. Xiao, S. Li, J. Q. Yu, J. Am. Chem. Soc.
2013, 125, 9322; b) C. Li, T. Yano, N. Ishida, M. Murakami, Angew.
Chem. Int. Ed. 2013, 52, 9801; Angew. Chem. 2013, 125, 9983; c) M.
Min, D. Kang, S. Jung, S. Hong, Adv. Synth. Catal. 2016, 358, 1296.
[20] a) Y. He, H. Wu, F. D. Toste, Chem. Sci. 2015, 6, 1194; b) R. S. Shaikh,
S. J. S. Düsel, B. König, ACS Catal. 2016, 6, 8410.
[21] Reviews on N–C amide cross-coupling: a) G. Meng, S. Shi, M.Szostak,
Synlett 2016, 27, 2530; b) C. Liu, M. Szostak, Chem. Eur. J. 2017, 23,
7157; c) J. E. Dander, N. K. Garg, ACS Catal. 2017, 7, 1413.
[22] A. Greenberg, C. M. Breneman, J. F.Liebman, The Amide Linkage:
Structural Significance in Chemistry, Biochemistry and Materials
Science; Wiley-VCH: New York, 2003.
[2]
[3]
[23] a) Metal-Catalyzed Cross-Coupling Reactions and More, A. de Meijere,
S. Bräse, M. Oestreich, Eds.; Wiley: New York, 2014; b) Science of
Synthesis: Cross-Coupling and Heck-Type Reactions, G. A. Molander,
J. P. Wolfe, M. Larhed, Eds.;Thieme: Stuttgart, 2013.
a) C. S. Demmer, N. K. Larsen, L. Bunch, Chem. Rev. 2011, 111, 7981;
b) P. Guga, Curr. Top. Med. Chem. 2007, 7, 695; c) K. Moonen, O.
Laureyn, C. V. Stevens, Chem. Rev. 2004, 104, 6177.
[4]
[5]
A. Börner, Phosphorus Ligands in Asymmetric Catalysis; Wiley:
Weinheim, 2008.
[24] Review on electrophilic activation of amides: a) D. Kaiser, N. Maulide, J.
Org. Chem. 2016, 81, 4421; For an excellent overview of amide cross-
coupling, see: b) S. A. Ruider, N. Maulide, Angew. Chem. 2015, 127,
14062; Angew. Chem. Int. Ed. 2015, 54, 13856; For select recent
examples of electrophilic activation of amides, see: c) A. de la Torre, D.
Kaiser, N. Maulide, J. Am. Chem. Soc. 2017, 139, 6578; d) V. Tona, A.
de la Torre, M. Padmanaban, S. Ruider, L. Gonzalez, N. Maulide, J.
Am. Chem. Soc. 2016, 138, 8348; e) D. Kaiser, A. de la Torre, S.
Shaaban, N. Maulide, Angew. Chem. Int. Ed. 2017, 129, 6015; Angew.
Chem. Int. Ed. 2017, 56, 5921; f) B. Peng, D. Geerdink, C. Fares, N.
Maulide, Angew. Chem. 2014, 126, 5566; Angew. Chem. Int. Ed. 2014,
53, 5462; g) B. Peng, X. Huang, L. G. Xie, N. Maulide, Angew. Chem.
2014, 126, 8862; Angew. Chem. Int. Ed. 2014, 53, 8718; h) B. Peng. D.
Geerdink, N. Maulide, J. Am. Chem. Soc. 2013, 135, 14968.
[25] L. Hie, N. F. F. Nathel, T. K. Shah, E. L. Baker, X. Hong, Y. F. Yang, P.
Liu, K. N. Houk, N. K. Garg, Nature 2015, 524, 79.
a) T. Hirao, T. Masunaga, Y. Ohshiro, T. Agawa, Synthesis 1981, 56; b)
T. Hirao, T. Masunaga, N. Yamada, Y. Ohshiro, T. Agawa, Bull. Chem.
Soc. Jpn. 1982, 55, 909; See also: c) T. Hirao, T. Masunaga, Y.
Ohshiro, T. Agawa, Tetrahedron Lett. 1980, 21,3595.
[6]
[7]
Reviews: a) A. L. Schwan, Chem. Soc. Rev. 2004, 33, 218; b) D. Prim,
J. M. Campagne, D. Joseph, B. Andrioletti, Tetrahedron 2002, 58,
2041; c) E. Jablonkai, G. Keglevich, Org. Prep. Proc. Int. 2014, 46, 281.
a) J. L. Montchamp, Y. R. Dumond, J. Am. Chem. Soc. 2001, 123, 510;
b) M. Kalek, A. Ziadi, J. Stawinski, Org. Lett. 2008, 10, 4637; c) Y.
Belabassi, S. Alzghari, J. L. Montchamp, J. Organomet. Chem. 2008,
693, 3171; d) A. J. Boomfield, S. B. Herzon, Org. Lett. 2012, 14, 4370;
e) E. L. Deal, C. Petit, J. L. Montchamp, Org. Lett. 2011, 13, 3270; f) O.
Berger, C. Petit, E. Deal, J. L. Montchamp, Adv. Synth. Catal. 2013,
355, 1361; g) M. Kalek, J. Stawinski, Organometallics 2008, 27, 5876;
h) M. Kalek, M. Jezowska, J. Stawinski, Adv. Synth. Catal. 2009, 351,
3207; i) E. Jablonkai, G. Keglevich, Tetrahedron Lett. 2013, 54, 4185.
For additional methods, see: Decarboxylative methods: j) J. Li, X. Bi, H.
Wang, J. Xiao, Asian J. Org. Chem. 2014, 3, 1113; k) Y. Wu, L. Liu, K.
[26] Acyl couplings: a) G. Meng, M. Szostak, Org. Lett. 2015, 17, 4364; b) G.
Meng, S. Shi, M. Szostak, ACS Catal. 2016, 6, 7335; c) P. Lei, G. Meng,
M. Szostak, ACS Catal. 2017, 7, 1960 and references cited therein.
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