Organic Letters
Letter
C. V. Angew. Chem., Int. Ed. 2005, 44, 7407−7411. (c) Laghzizil, A.;
Elhrech, N.; Britel, O.; Bouhaouss, A.; Ferhat, M. J. Fluorine Chem. 2000,
101, 69−73. (d) Moiseev, D. V.; Patrick, B. O.; James, B. R. Inorg. Chem.
2007, 46, 11467−11474. (e) Luo, X.; Zhou, Z.; Li, X.; Liang, X.; Ye, J.
RSC Adv. 2011, 1, 698−705. (f) Zhao, D.; Yuan, Y.; Chan, A. S. C.;
Wang, R. Chem. - Eur. J. 2009, 15, 2738−2741. (g) Simoni, D.; Invidiata,
F. P.; Manferdini, M.; Lampronti, I.; Rondanin, R.; Roberti, M.; Pollini,
G. P. Tetrahedron Lett. 1998, 39, 7615−7618. (h) Li, G.; Wang, L.; Yao,
Z.; Xu, F. Tetrahedron: Asymmetry 2014, 25, 989−996. (i) Strappaveccia,
G.; Bianchi, L.; Ziarelli, S.; Santoro, S.; Lanari, D.; Pizzo, F.; Vaccaro, L.
Org. Biomol. Chem. 2016, 14, 3521−3525. (j) Wen, S.; Li, P.; Wu, H.; Yu,
F.; Liang, X.; Ye, J. Chem. Commun. 2010, 46, 4806−4808. (k) Russo, A.;
Lattanzi, A. Eur. J. Org. Chem. 2010, 2010, 6736−6739. (l) Rai, V.;
Namboothiri, I. N. N. Tetrahedron: Asymmetry 2008, 19, 2335−2338.
(m) Zhu, Y.; Malerich, J. P.; Rawal, V. H. Angew. Chem., Int. Ed. 2010, 49,
153−156. (n) Fu, X.; Jiang, Z.; Tan, C.-H. Chem. Commun. 2007, 5058−
5060. (o) Wang, J.; Heikkinen, L. D.; Li, H.; Zu, L.; Jiang, W.; Xie, H.;
Wang, W. Adv. Synth. Catal. 2007, 349, 1052−1056. (p) Lenker, H. K.;
Richard, M. E.; Reese, K. P.; Carter, A. F.; Zawisky, J. D.; Winter, E. F.;
Bergeron, T. W.; Guydon, K. S.; Stockland, R. A. J. Org. Chem. 2012, 77,
1378−1385. (q) Li, Z.; Ni, Y.; Qiu, F.; Ying, A.; Xu, S.; Wang, Y. Catal.
Lett. 2014, 144, 1810−1818. (r) Sobhani, S.; Bazrafshan, M.; Delluei, A.
A.; Parizi, Z. P. Appl. Catal., A 2013, 454, 145−151. (s) Sobhani, S.;
Parizi, Z. P.; Rezazadeh, S. J. Organomet. Chem. 2011, 696, 813−817.
(t) Hosseini-Sarvari, M.; Etemad, S. Tetrahedron 2008, 64, 5519−5523.
(3) (a) Demmer, C. S.; Krogsgaard-Larsen, N.; Bunch, L. Chem. Rev.
2011, 111, 7981−8006. (b) Olszewski, T. K. Synthesis 2014, 46, 403−
429. (c) Palacios, F.; Olszewski, T. K.; Vicario, J. Org. Biomol. Chem.
2010, 8, 4255−4258. (d) Michalska, J.; Boduszek, B.; Olszewski, T. K.
Heteroat. Chem. 2011, 22, 617−624. (e) Olszewski, T. K.; Majewski, M.
Tetrahedron: Asymmetry 2015, 26, 846−852. (f) Olszewski, T. K.
Tetrahedron: Asymmetry 2015, 26, 393−399. (g) Olszewski, T. K.;
Scheme 6. Synthetic Utility of Phospha-Michael Adduct 3a
Finally, treatment of 3a with NH2OH·HCl provided β-
oximephosphonate 4f in high yield (86%).
In summary, we have developed a new catalytic phospha-
Michael addition protocol for the synthesis of γ-ketodiaza-
phosphonates by NHP-promoted pathway under nucleophilic
additive-free reaction conditions. This method tolerated a wide
range of functional groups on α,β-unsaturated aldehydes and was
compatible with various α,β-unsaturated ketones. This study, for
the first time, demonstrated the multiplex and critical roles of
Brønsted acid motif in the phospha-Michael addition reaction,
such as an internal nucleophile promoting the transformation of
P(III) to P(V), a directing group achieving a complete
chemoselectivity (1,4-addition), and an activator enabling α,β-
unsaturated ketones to form iminium intermediates for direct
phosphonylation. Moreover, synthetic utility of this phospha-
Michael adduct was demonstrated. Further studies to find more
efficient C−P bond formation based on the NHP-mediated
systems are underway.
́
Wojaczynska, E.; Wieczorek, R.; Bąkowicz, J. Tetrahedron: Asymmetry
2015, 26, 601−607.
(4) Kluender, H.; Benz, G.; Brittelli, D.; Bullock, W.; Combs, K.;
Dixon, B.; Schneider, S.; Wood, J.; Vanzandt, M.; Wolanin, D. US Pat.
Appl. US 95-539409951106, 1998; Chem. Abstr. 1998, 161412.
(5) Schwender, C. F.; Beers, S. A.; Malloy, E.; Demarest, K.; Minor, L.;
Lau, K. H. W. Bioorg. Med. Chem. Lett. 1995, 5, 1801−1806.
(6) (a) Jomaa, H.; Wiesner, J.; Sanderbrand, S.; Altincicek, B.;
ASSOCIATED CONTENT
* Supporting Information
■
S
Weidemeyer, C.; Hintz, M.; Turbachova, I.; Eberl, M.; Zeidler, J.;
̈
The Supporting Information is available free of charge on the
Lichtenthaler, H. K.; Soldati, D.; Beck, E. Science 1999, 285, 1573−1576.
(b) Andaloussi, M.; Henriksson, L. M.; Wieç kowska, A.; Lindh, M.;
Bjorkelid, C.; Larsson, A. M.; Suresh, S.; Iyer, H.; Srinivasa, B. R.;
̈
Experimental details (PDF)
Spectral data of all new compounds (PDF)
́
Bergfors, T.; Unge, T.; Mowbray, S. L.; Larhed, M.; Jones, T. A.; Karlen,
A. J. Med. Chem. 2011, 54, 4964−4976.
(7) Ikemura, K.; Tay, F. R.; Nishiyama, N.; Pashley, D. H.; Endo, T.
Dent. Mater. J. 2006, 25, 566−575.
AUTHOR INFORMATION
Corresponding Author
■
(8) (a) Mulla, K.; Aleshire, K. L.; Forster, P. M.; Kang, J. Y. J. Org.
Chem. 2016, 81, 77−88. (b) Mulla, K.; Kang, J. Y. J. Org. Chem. 2016, 81,
4550−4558.
Notes
(9) Focken, T.; Hanessian, S. Beilstein J. Org. Chem. 2014, 10, 1848−
1877.
The authors declare no competing financial interest.
(10) For the full optimized reaction conditions, see the Supporting
ACKNOWLEDGMENTS
■
(11) Thiazolidine byproduct D was isolated in 82% yield.
(12) (a) Wang, F.; Wang, S.; Zhu, X.; Zhou, S.; Miao, H.; Gu, X.; Wei,
Y.; Yuan, Q. Organometallics 2013, 32, 3920−3931. (b) Zhang, A.; Cai,
L.; Yao, Z.; Xu, F.; Shen, Q. Heteroat. Chem. 2013, 24, 345−354.
(13) Dalcanale, E.; Montanari, F. J. Org. Chem. 1986, 51, 567−569.
(14) Braunstein, P.; Naud, F. Angew. Chem., Int. Ed. 2001, 40, 680−
699.
This work was supported by University of Nevada Las Vegas
(Faculty Opportunity Awards). Dr. Karimulla Mulla (Emory
University) is acknowledged for his early, related work. Dr.
Katarzyna Lorenc-Kukula (SCAAC) is acknowledged for mass
spectra data.
REFERENCES
■
(1) (a) Trost, B. M. Science 1991, 254, 1471−1477. (b) Trost, B. M.
Angew. Chem., Int. Ed. Engl. 1995, 34, 259−281. (c) Rulev, A. Y. RSC
Adv. 2014, 4, 26002−26012. (d) Enders, D.; Saint-Dizier, A.; Lannou,
M.-I.; Lenzen, A. Eur. J. Org. Chem. 2006, 2006, 29−49.
(2) (a) Maerten, E.; Cabrera, S.; Jørgensen, K. A. J. Org. Chem. 2007,
́
72, 8893−8903. (b) Moonen, K.; Van Meenen, E.; Verwee, A.; Stevens,
D
Org. Lett. XXXX, XXX, XXX−XXX