Organometallics
Communication
(3) Ogliaruso, M. A.; Wolfe, J. F.; Patai, S.; Rappoport, Z. In Synthesis
of lactones and lactams; Patai, S., Rappoport, Z., Eds.; Wiley:
Chichester, U.K., 1993.
Regeneration of 1 was achieved by the reaction of bis(μ-
hydroxo) complex 3 with atmospheric dihydrogen, and 1 was
obtained in 69% yield. Since 1 was not regenerated smoothly in
the catalysis conducted under an Ar atmosphere, accumulation
of H2 is required for the smooth turnover of the catalytic cycle,
which might explain why the addition of H2 shortened the
induction period.
In conclusion, a catalytic dehydrogenative oxidation of cyclic
amines was achieved using a diruthenium complex. The
stoichiometric reaction using a seven-membered cyclic amine
and water revealed that the perpendicularly coordinated
imidoyl complex generated by the N−H and double C−H
bond cleavage was a key intermediate for the formation of the
lactam. Some side reactions were observed for the reactions
with five- and six-membered cyclic amines, and further details
of the reaction mechanisms will be reported in the future. We
believe that the double C−H bond activation at the α position
of the heteroatom using cluster compounds will lead to new
series of direct functionalization methods.
(4) (a) Moriarty, R. M.; Vaid, R. K.; Duncan, M. P.; Ochiai, M.;
Inenaga, M.; Nagao, Y. Tetrahedron Lett. 1988, 29, 6913−6916.
(b) Tsuboi, S.; Ishii, N.; Sakai, T.; Tari, I.; Utaka, M. Bull. Chem. Soc.
Jpn. 1990, 63, 1888−1893. (c) Chandrakala, M.; Murthy, K. V. V. S. B.
S. R.; Kulkami, S. J.; Raghavan, K. V. Indian J. Chem. 2000, 39B, 71−
73. (d) Tada, N.; Miyamoto, K.; Ochiai, M. Chem. Pharm. Bull. 2004,
52, 1143−1144. (e) Dairo, T. O.; Nelson, N. C.; Slowing, I. I.;
Angelici, R. J.; Woo, L. K. Catal. Lett. 2016, 146, 2278−2291. (f) Jin,
X.; Kataoka, K.; Yatabe, T.; Yamaguchi, K.; Mizuno, N. Angew. Chem.,
Int. Ed. 2016, 55, 7212−7217.
(5) (a) Khusnutdinova, J. R.; Ben-David, Y.; Milstein, D. J. Am. Chem.
Soc. 2014, 136, 2998−3001. (b) Gellrich, U.; Khusnutdinova, J. R.;
Leitus, G. M.; Milstein, D. J. Am. Chem. Soc. 2015, 137, 4851−4859.
(6) For example: (a) Akagi, F.; Matsuo, T.; Kawaguchi, H. Angew.
Chem., Int. Ed. 2007, 46, 8778−8781. (b) Fryzuk, M. D. Acc. Chem.
Res. 2009, 42, 127−133. (c) Takao, T.; Suzuki, H. Coord. Chem. Rev.
2012, 256, 695−708. (d) Shima, T.; Hu, S.; Luo, G.; Kang, X.; Luo, Y.;
Hou, Z. Science 2013, 340, 1549−1552. (e) Shimogawa, R.; Takao, T.;
Konishi, G.; Suzuki, H. Organometallics 2014, 33, 5066−5069. (f) Hu,
S.; Shima, T.; Hou, Z. Nature 2014, 512, 413−415. (g) Takao, T.;
Suzuki, H. Bull. Chem. Soc. Jpn. 2014, 87, 443−458.
ASSOCIATED CONTENT
* Supporting Information
■
S
(7) (a) Suss-Fink, G.; Jenke, T.; Heitz, H.; Pellinghelli, M. A.;
̈
The Supporting Information is available free of charge on the
Tiripicchio, A. J. J. Organomet. Chem. 1989, 379, 311−323. (b) Day,
M. W.; Hajela, S.; Kabir, S. E.; Irving, M.; McPhillips, T.; Wolf, E.;
Hardcastle, K. I.; Rosenberg, E.; Milone, L.; Gobetto, R.; Osella, D.
Organometallics 1991, 10, 2743−2751. (c) Adams, R. D.; Chen, G.
Organometallics 1993, 12, 2070−2077. (d) Day, M.; Espitia, D.;
Hardcastle, K. I.; Kabir, S. E.; McPhillips, T.; Rosenberg, E.; Gobetto,
R.; Milone, L.; Osella, D. Organometallics 1993, 12, 2309−2324.
(e) Cifuentes, M. P.; Humphrey, M. G.; Skelton, B. W.; White, A. H. J.
J. Organomet. Chem. 1993, 458, 211−218. (f) Kabir, S. E.; Rosenberg,
E.; Day, M.; Hardcastle, K. I.; Irving, M. J. Cluster Sci. 1994, 5, 481−
503.
Experimental details, crystal data and results of XRD
studies of 2−5, VT-1H NMR spectrum of 2, and NMR
Accession Codes
lographic data for this paper. These data can be obtained free of
Cambridge Crystallographic Data Centre, 12, Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
(8) (a) Kabir, S. E.; Rosenberg, E.; Day, M.; Hardcastle, K. I.
Organometallics 1994, 13, 4437−4447. (b) Rosenberg, E.; Milone, L.;
Gobetto, R.; Osella, D.; Hardcastle, K.; Hajela, S.; Moizeau, K.; Day,
M.; Wolf, E.; Espitia, D. Organometallics 1997, 16, 2665−2673.
(c) Kabir, S. E.; Rosenberg, E.; Milone, L.; Gobetto, R.; Osella, D.;
Ravera, M.; McPhillips, T.; Day, M. W.; Carlot, D.; Hajela, S.; Wolf, E.;
Hardcastle, K. Organometallics 1997, 16, 2674−2681.
(9) (a) Yanagi, T.; Suzuki, H.; Oishi, M. Chem. Lett. 2013, 42, 1403−
1405. (b) Shimogawa, R.; Takao, T.; Suzuki, H. Organometallics 2014,
33, 289−301. (c) Shimogawa, R.; Takao, T.; Suzuki, H. J. Organomet.
Chem. 2016, 801, 6−9.
AUTHOR INFORMATION
Corresponding Author
■
ORCID
Notes
(10) Suzuki, H.; Omori, H.; Lee, D. H.; Yoshida, Y.; Fukushima, M.;
Tanaka, M.; Moro-oka, Y. Organometallics 1994, 13, 1129−1146.
(11) Shimogawa, R.; Konishi, G.; Takao, T.; Suzuki, H. Organo-
metallics 2016, 35, 1446−1457.
The authors declare no competing financial interest.
(12) Fryzuk, M. D.; Piers, W. E. Organometallics 1990, 9, 986−998.
(13) Suzuki, H.; Kakigano, T.; Igarashi, M.; Usui, A.; Noda, K.;
Oshima, M.; Tanaka, M.; Moro-oka, Y. Chem. Lett. 1993, 22, 1707−
1710.
(14) (a) Takao, T.; Kawashima, T.; Matsubara, K.; Suzuki, H.
Organometallics 2005, 24, 3371−3374. (b) Kawashima, T.; Takao, T.;
Suzuki, H. Angew. Chem., Int. Ed. 2006, 45, 485−488. (c) Kanda, H.;
Kawashima, T.; Takao, T.; Suzuki, H. Organometallics 2012, 31, 1917−
1926.
ACKNOWLEDGMENTS
■
This work was supported by JST ACT-C Grant Number
JPMJCR12YA, Japan. This work was also supported by a
Grant-in-Aid for JSPS Fellows grant number 26009727. R.S.
thanks the JSPS Research Fellowship for Young Scientists for
financial support.
REFERENCES
■
(15) (a) Feng, Q.; Ferrer, M.; Green, M. L. H.; McGowan, P. C.;
Mountford, P.; Mtetwa, V. S. B. J. Chem. Soc., Chem. Commun. 1991,
552−554. (b) Tayebani, M.; Gambarotta, S.; Yap, G. Organometallics
(1) For example: (a) Jazzar, R.; Hitce, J.; Renaudat, A.; Sofack-
Kreutzer, J.; Baudoin, O. Chem. - Eur. J. 2010, 16, 2654−2672.
(b) Rouquet, G.; Chatani, N. Angew. Chem., Int. Ed. 2013, 52, 11726−
11743 and references therein.
1998, 17, 3639−3641. (c) Alvarez, M. A.; García, M. E.; García-Vivo,
́
D.; Ruiz, M. A.; Vega, M. F. Organometallics 2013, 32, 4543−4555.
(2) For example: (a) Chen, M. S.; White, M. C. Science 2007, 318,
783−787. (b) Correa, A.; Mancheno, O. G.; Bolm, C. Chem. Soc. Rev.
̃
2008, 37, 1108−1117. (c) Sun, C.-L.; Li, B.-J.; Shi, Z.-J. Chem. Rev.
2011, 111, 1293−1314. (d) Yeung, C. S.; Dong, V. M. Chem. Rev.
2011, 111, 1215−1292 and references therein.
D
Organometallics XXXX, XXX, XXX−XXX