Organometallics
Article
(7) Valente, C.; Calimsiz, S.; Hoi, K. H.; Mallik, D.; Sayah, M.;
Organ, M. G. Angew. Chem., Int. Ed. 2012, 51, 3314−3332.
(8) (a) Chartoire, A.; Frogneux, X.; Nolan, S. P. Adv. Synth. Catal.
2012, 354, 1897−1901. (b) Chartoire, A.; Lesieur, M.; Falivene, L.;
Slawin, A. M. Z.; Cavallo, L.; Cazin, C. S. J.; Nolan, S. P. Chem.−Eur. J.
2012, 18, 4517−4521.
AUTHOR INFORMATION
■
Corresponding Author
Notes
The authors declare no competing financial interest.
(9) Meiries, S.; Chartoire, A.; Slawin, A. M. Z.; Nolan, S. P.
Organometallics 2012, 31, 3402−3409.
ACKNOWLEDGMENTS
(10) Altenhoff, G.; Goddard, R.; Lehmann, C. W.; Glorius, F. Angew.
Chem., Int. Ed. 2003, 42, 3690−3693.
(11) For the first reported synthesis of IPr, see: Huang, J.; Nolan, S.
P. J. Am. Chem. Soc. 1999, 121, 9889−9890.
(12) Berthon-Gelloz, G.; Siegler, M. A.; Spek, A. L.; Tinant, B.; Reek,
J. N. H.; Marko, I. E. Dalton Trans. 2010, 39, 1444−1446.
(13) Organ reports receiving IPent·HCl from Total Synthesis Ltd.
and has never, to the best of our knowledge, reported the preparation
of the salt.
■
We gratefully acknowledge the EC for funding through the
seventh framework program SYNFLOW. Umicore AG is
thanked for its generous gifts of materials. S.P.N. is a Royal
Society Wolfson Research Merit Award holder.
REFERENCES
■
(1) (a) Navarro, O.; Kelly, R. A., III; Nolan, S. P. J. Am. Chem. Soc.
2003, 125, 16194−16195. (b) Viciu, M. S.; Kelly, R. A., III; Stevens, E.
D.; Naud, F.; Studer, M.; Nolan, S. P. Org. Lett. 2003, 5, 1479−1482.
(c) Navarro, O.; Marion, N.; Oonishi, Y.; Kelly, R. A., III; Nolan, S. P.
J. Org. Chem. 2006, 71, 685−692. (d) Broggi, J.; Clavier, H.; Nolan, S.
P. Organometallics 2008, 27, 5525−5531.
(2) (a) Kantchev, E. A. B.; Peh, G.-R.; Zhang, C.; Ying, J. Y. Org. Lett.
2008, 10, 3949−3952. (b) Kantchev, E. A. B.; Ying, J. Y.
Organometallics 2009, 28, 289−299. (c) Peh, G.-R.; Kantchev, E. A.
B.; Zhang, C.; Ying, J. Y. Org. Biomol. Chem. 2009, 7, 2110−2119.
(3) (a) Chen, M.-T.; Vicic, D. A.; Chain, W. J.; Turner, M. L.;
Navarro, O. Organometallics 2011, 30, 6770−6773. (b) Chen, M.-T.;
Vicic, D. A.; Turner, M. L.; Navarro, O. Organometallics 2011, 30,
5052−5056.
(4) (a) Tang, Y.-Q.; Lu, J.-M.; Shao, L.-X. J. Organomet. Chem. 2011,
696, 3741−3744. (b) Zhou, X.-X.; Shao, L.-X. Synthesis 2011, 3138−
3142. (c) Zhu, L.; Gao, T.-T.; Shao, L.-X. Tetrahedron 2011, 67,
5150−5155. (d) Gu, Z.-S.; Shao, L.-X.; Lu, J.-M. J. Organomet. Chem.
2012, 700, 132−134. (e) Xiao, Z.-K.; Shao, L.-X. Synthesis 2012, 44,
711−716. (f) Zhu, L.; Ye, Y.-M.; Shao, L.-X. Tetrahedron 2012, 68,
2414−2420.
(5) (a) O’Brien, C. J.; Kantchev, E. A. B.; Valente, C.; Hadei, N.;
Chass, G. A.; Lough, A.; Hopkinson, A. C.; Organ, M. G. Chem.−Eur.
J. 2006, 12, 4743−4748. (b) Organ, M. G.; Abdel-Hadi, M.; Avola, S.;
Hadei, N.; Nasielski, J.; O’Brien, C. J.; Valente, C. Chem.−Eur. J. 2006,
13, 150−157. (c) Organ, M. G.; Avola, S.; Dubovyk, I.; Hadei, N.;
Kantchev, E. A. B.; O’Brien, C. J.; Valente, C. Chem.−Eur. J. 2006, 12,
4749−4755. (d) Organ, M. G.; Abdel-Hadi, M.; Avola, S.; Dubovyk, I.;
Hadei, N.; Kantchev, E. A. B.; O’Brien, C. J.; Sayah, M.; Valente, C.
Chem.−Eur. J. 2008, 14, 2443−2452. (e) Organ, M. G.; Calimsiz, S.;
Sayah, M.; Hoi, K. H.; Lough, A. J. Angew. Chem., Int. Ed. 2009, 48,
2383−2387. (f) Calimsiz, S.; Sayah, M.; Mallik, D.; Organ, M. G.
Angew. Chem., Int. Ed. 2010, 49, 2014−2017. (g) Dowlut, M.; Mallik,
D.; Organ, M. G. Chem.−Eur. J. 2010, 16, 4279−4283. (h) Nasielski,
J.; Hadei, N.; Achonduh, G.; Kantchev, E. A. B.; O’Brien, C. J.; Lough,
A.; Organ, M. G. Chem.−Eur. J. 2010, 16, 10844−10853. (i) Valente,
C.; Belowich, M. E.; Hadei, N.; Organ, M. G. Eur. J. Org. Chem. 2010,
4343−4354. (j) Calimsiz, S.; Organ, M. G. Chem. Commun. 2011, 47,
5181−5183. (k) Hoi, K. H.; Calimsiz, S.; Froese, R. D. J.; Hopkinson,
A. C.; Organ, M. G. Chem.−Eur. J. 2011, 17, 3086−3090. (l) Hoi, K.
H.; Calimsiz, S.; Froese, R. D. J.; Hopkinson, A. C.; Organ, M. G.
Chem.−Eur. J. 2012, 18, 145−151.
(14) (a) Kosugi, M.; Kameyama, M.; Migita, T. Chem. Lett. 1983,
927−928. (b) Guram, A. S.; Rennels, R. A.; Buchwald, S. L. Angew.
Chem., Int. Ed. Engl. 1995, 34, 1348−1350. (c) Louie, J.; Hartwig, J. F.
Tetrahedron Lett. 1995, 36, 3609−3612. (d) Hartwig, J. F. In
Handbook of Organopalladium Chemistry Organic Synthesis; Wiley-
Interscience: New York, 2002; Vol. 1, pp 1051−1096. (e) Muci, A. R.;
Buchwald, S. L. Top. Curr. Chem. 2002, 219, 131−209. (f) Bedford, R.
B.; Cazin, C. S. J.; Holder, D. Coord. Chem. Rev. 2004, 248, 2283−
2321. (g) Jiang, L.; Buchwald, S. L. In Metal-Catalyzed Cross-Coupling
Reactions, 2nd ed.; Wiley-VCH: Weinheim, 2004; Vol. 2, pp 699−760.
(h) Hartwig, J. F. Acc. Chem. Res. 2008, 41, 1534−1544. (i) Marion,
N.; Nolan Steven, P. Acc. Chem. Res. 2008, 41, 1440−1449.
(j) Fortman, G. C.; Nolan, S. P. Chem. Soc. Rev. 2011, 40, 5151−5169.
(15) CCDC-893280 (1) contains the supplementary crystallographic
data for this contribution. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via www.ccdc.cam.
(16) Weber, S. G.; Loos, C.; Rominger, F.; Straub, B. F. ARKIVOC
2012, 226−242.
(17) The bond length between the Pd and the central carbon atom of
the NHC has been fixed at 2.00 Å in those calculations, in order to
compare efficiently the bulk of the various ligands. Sphere radius = 3.5
Å, mesh spacing = 0.05, H atoms were excluded, Bondi radii scaled by
1.17.
(b) Clavier, H.; Correa, A.; Cavallo, L.; Escudero-Adan, E. C.;
Benet-Buchholz, J.; Slawin, A. M. Z.; Nolan, S. P. Eur. J. Inorg. Chem.
2009, 1767−1773. (c) Poater, A.; Cosenza, B.; Correa, A.; Giudice, S.;
Ragone, F.; Scarano, V.; Cavallo, L. Eur. J. Inorg. Chem. 2009, 1759−
1766. (d) Clavier, H.; Nolan, S. P. Chem. Commun. 2010, 46, 841−
861.
(19) See Supporting Information for more information about
optimization reactions.
(6) For other examples of [Pd-NHC] complexes stabilized by
ancillary nitrogen ligands see: (a) Iyer, S.; Jayanthi, A. Synlett 2003,
1125−1128. (b) Iyer, S.; Kulkarni, G. M.; Ramesh, C. Tetrahedron
2004, 60, 2163−2172. (c) Li, J.; Cui, M.; Yu, A.; Wu, Y. J. Organomet.
Chem. 2007, 692, 3732−3742. (d) Jin, Z.; Qiu, L.-L.; Li, Y.-Q.; Song,
H.-B.; Fang, J.-X. Organometallics 2010, 29, 6578−6586. (e) Ren, G.;
Cui, X.; Wu, Y. Eur. J. Org. Chem. 2010, 2372−2378. (f) Ren, G.; Cui,
X.; Yang, E.; Yang, F.; Wu, Y. Tetrahedron 2010, 66, 4022−4028.
(g) Zhang, J.; Yang, X.; Cui, X.; Wu, Y. Tetrahedron 2011, 67, 8800−
8807. (h) Xu, C.; Li, H.-M.; Liu, H.; Zhang, Z.-Q.; Wang, Z.-Q.; Fu,
W.-J.; Zhang, Y.-Q. Inorg. Chim. Acta 2012, 386, 22−26.
E
dx.doi.org/10.1021/om300725f | Organometallics XXXX, XXX, XXX−XXX