Journal of the American Chemical Society
Communication
K. Organometallics 2006, 25, 3599. (d) Diesendruck, C. E.; Tzur, E.;
Ben-Asuly, A.; Goldberg, I.; Straub, B. F.; Lemcoff, N. G. Inorg. Chem.
2009, 48, 10819. (e) Tzur, E.; Szadkowska, A.; Ben-Asuly, A.; Makal, A.;
Goldberg, I.; Wozniak, K.; Grela, K.; Lemcoff, N. G. Chem.Eur. J.
2010, 16, 8726. For a mechanistic study of syn/anti isomerization, see:
(f) Poater, A.; Ragone, F.; Correa, A.; Szadkowska, A.; Barbasiewicz, M.;
Grela, K.; Cavallo, L. Chem.Eur. J. 2010, 16, 14354.
ASSOCIATED CONTENT
* Supporting Information
Procedures and additional data. This material is available free of
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S
AUTHOR INFORMATION
Corresponding Author
■
(10) Polar solvents have been proposed to stabilize the high dipole
moment of syn alkene−NHC complexes and the related metal-
lacyclobutanes. See: (a) Benitez, D.; Goddard, W. A., III. J. Am. Chem.
Soc. 2005, 127, 12218. (b) Correa, A.; Cavallo, L. J. Am. Chem. Soc. 2006,
128, 13352.
Author Contributions
†R.K.M.K. and S.T. contributed equally.
(11) For the significance of minimizing donor−donor interactions in
Ru-catalyzed olefin metathesis, see: Khan, R. K. M.; Zhugralin, A. R.;
Torker, S.; O’Brien, R. V.; Lombardi, P. J.; Hoveyda, A. H. J. Am. Chem.
Soc. 2012, 134, 12438.
(12) For mechanistic investigations of favored reaction pathways
through density functional theory (DFT) calculations, see: (a) Vyboish-
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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Financial support was provided by the NSF (CHE-1111074).
R.K.M.K. and S.T. acknowledge LaMattina Graduate and Swiss
NSF Postdoctoral Fellowships, respectively. We thank Dr. Bo Li
for assistance with obtaining X-ray data.
chikov, S. F.; Buhl, M.; Thiel, W. Chem.Eur. J. 2002, 8, 3962.
̈
(b) Adlhart, C.; Chen, P. J. Am. Chem. Soc. 2004, 126, 3496. (c) Straub,
B. F. Adv. Synth. Catal. 2007, 349, 204. (d) Benitez, D.; Tkatchouk, E.;
Goddard, W. A., III. Chem. Commun. 2008, 6194. For spectroscopic
studies, see: (e) van der Eide, E. F.; Romero, P. E.; Piers, W. E. J. Am.
Chem. Soc. 2008, 130, 4485. (f) Wenzel, A. G.; Blake, G.; VanderVelde,
D. G.; Grubbs, R. H. J. Am. Chem. Soc. 2011, 133, 6429.
REFERENCES
■
(1) For a comprehensive review of the synthesis of Z alkenes, see: Siau,
W.-Y.; Zhang, Y.; Zhao, Y. Top. Curr. Chem. 2012, 327, 33.
(13) DFT calculations have suggested that low Z selectivities may
result from anti (to NHC) modes of alkene addition. See: Bahri-Laleh,
N.; Credendino, R.; Cavallo, L. Beilstein J. Org. Chem. 2011, 7, 40.
(14) For attempts to achieve stereoselectivity by an anti pathway, see:
(a) Vehlow, K.; Maechling, S.; Blechert, S. Organometallics 2006, 25, 25.
(b) Ledoux, N.; Linden, A.; Allaert, B.; Mierde, H. V.; Verpoort, F. Adv.
Synth. Catal. 2007, 349, 1692. (c) Vougioukalakis, G. C.; Grubbs, R. H. J.
Am. Chem. Soc. 2008, 130, 2234. (d) Anderson, D. R.; Ung, T.;
Mkrtumyan, G.; Bertrand, G.; Grubbs, R. H.; Schrodi, Y. Organometallics
2008, 27, 563. (e) Rosen, E. L.; Sung, D. H.; Chen, Z.; Lynch, V. M.;
Bielawski, C. W. Organometallics 2010, 29, 250. (f) Peeck, L. H.;
(2) For an overview of problems in catalytic olefin metathesis, see:
(a) Zhugralin, A. R.; Hoveyda, A. H. Nature 2007, 450, 243. For selected
reviews of various aspects of catalytic olefin metathesis, see: (b) Schrock,
R. R.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2003, 42, 4592.
(c) Handbook of Metathesis; Grubbs, R. H., Ed.; Wiley-VCH: Weinheim,
Germany, 2003. (d) Hoveyda, A. H.; Gillingham, D. G.; Van
Veldhuizen, J. J.; Kataoka, O.; Garber, S. B.; Kingsbury, K. S.; Harrity,
J. P. A. Org. Biomol. Chem. 2004, 2, 8. (e) Lozano-Vila, A. M.; Monsaert,
S.; Bajek, A.; Verpoort, F. Chem. Rev. 2010, 110, 4865.
(3) (a) Ibrahem, I.; Yu, M.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem.
Soc. 2009, 131, 3844. (b) Flook, M. M.; Jiang, A. J.; Schrock, R. R.;
Leuthausser, S.; Plenio, H. Organometallics 2010, 29, 4339.
̈
Muller, P.; Hoveyda, A. H. J. Am. Chem. Soc. 2009, 131, 7962. (c) Meek,
̈
(15) (a) Monfette, S.; Fogg, D. E. Organometallics 2006, 25, 1940.
(b) Monfette, S.; Camm, K. D.; Gorelsky, S. I.; Fogg, D. E.
Organometallics 2009, 28, 944. (c) Monfette, S.; Silva, J. A. D.;
Gorelsky, S. I.; Dalgarno, S. J.; dos Santos, E. N.; Araujo, M. H.; Fogg, D.
E. Can. J. Chem. 2009, 87, 361.
S. J.; O’Brien, R. V.; Llaveria, J.; Schrock, R. R.; Hoveyda, A. H. Nature
2011, 471, 461. (d) Yu, M.; Wang, C.; Kyle, A. F.; Jakubec, P.; Dixon, D.
J.; Schrock, R. R.; Hoveyda, A. H. Nature 2011, 479, 88. (e) Yu, M.;
Ibrahem, I.; Hasegawa, M.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem.
Soc. 2012, 134, 2788. (f) Wang, C.; Haeffner, F.; Schrock, R. R.;
Hoveyda, A. H. Angew. Chem., Int. Ed. 2013, 52, 1939. (g) Wang, C.; Yu,
M.; Kyle, A. F.; Jakubec, P.; Dixon, D. J.; Schrock, R. R.; Hoveyda, A. H.
Chem.Eur. J. 2013, 19, 2726. (h) Kiesewetter, E. T.; O’Brien, R. V.;
Yu, E. C.; Meek, S. J.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc.
2013, 135, 6026.
(16) (a) Garber, S. B.; Kingsbury, J. S.; Gray, B. L.; Hoveyda, A. H. J.
Am. Chem. Soc. 2000, 122, 8168. (b) Reference 2d.
(17) The dipole moments (μ) of complexes 1, 5, 6a, and 6b and the
energies of (E)- and (Z)-11a were calculated at the BP86/basis1 level.
See the Supporting Information for details.
(18) For the isolation of a Ru complex with an alkene coordinated syn
to the NHC, see: Anderson, D. R.; Hickstein, D. D.; O’Leary, D. J.;
Grubbs, R. H. J. Am. Chem. Soc. 2006, 128, 8386.
(19) Initial studies suggested that catecholate complex 5 decomposes
more readily and that the observed lack of selectivity might therefore be
spurious; efforts to elucidate these and related issues are underway.
(20) For Z-selective ROMPs of 7 and 9 with Mo-based alkylidenes,
see: (a) Reference 3b. (b) Yuan, J.; Schrock, R. R.; Gerber, L. C. H.;
(4) Torker, S.; Muller, A.; Chen, P. Angew. Chem., Int. Ed. 2010, 49,
3762.
̈
(5) (a) Endo, K.; Grubbs, R. H. J. Am. Chem. Soc. 2011, 133, 8525.
(b) Keitz, B. K.; Endo, K.; Herbert, M. B.; Grubbs, R. H. J. Am. Chem.
Soc. 2011, 133, 9686. (c) Keitz, B. K.; Endo, K.; Patel, P. R.; Herbert, M.
B.; Grubbs, R. H. J. Am. Chem. Soc. 2012, 134, 693. (d) Liu, P.; Xu, X.;
Dong, X.; Keitz, B. K.; Herbert, M. B.; Grubbs, R. H.; Houk, K. N. J. Am.
Chem. Soc. 2012, 134, 1464. (e) Khan, R. K. M.; O’Brien, R. V.; Torker,
S.; Li, B.; Hoveyda, A. H. J. Am. Chem. Soc. 2012, 134, 12774.
Muller, P.; Smith, S. Organometallics 2013, 32, 2983.
̈
(21) The actual Z selectivity in ROMP of 9 is less than the reported
value, since only one of the two alkenes undergoes reaction.
(22) Keitz, B. K.; Fedorov, A.; Grubbs, R. H. J. Am. Chem. Soc. 2012,
134, 2040.
(6) Occhipinti, G.; Hansen, F. R.; Tornroos, K. W.; Jensen, V. R. J. Am.
Chem. Soc. 2013, 135, 3331.
̈
(7) Hoveyda, A. H.; Malcolmson, S. J.; Meek, S. J.; Zhugralin, A. R.
Angew. Chem., Int. Ed. 2010, 49, 34.
(8) (a) Dias, E. L.; Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1997,
119, 3887. (b) Sanford, M. S.; Love, J. A.; Grubbs, R. H. J. Am. Chem. Soc.
2001, 123, 6543.
(9) Syn orientation of a donor group and an NHC ligand in
dichlororuthenium complexes has been observed, likely arising from
donor properties of the chelating units. For example, see: (a) Ung, T.;
Hejl, A.; Grubbs, R. H.; Schrodi, Y. Organometallics 2004, 23, 5399.
(b) Slugovc, C.; Perner, B.; Stelzer, F.; Mereiter, K. Organometallics
2004, 23, 3622. (c) Barbasiewicz, M.; Szadkowska, A.; Bujok, R.; Grela,
(23) The elevated temperature (vs 22 °C) and catalyst loading (vs 1.0
mol %) required in this case might be a consequence of intramolecular
chelation of the Ru center with the benzyloxy group, which would
decrease the catalyst activity.
(24) Free energy (ΔG) surfaces were computed at the ωB97XD/
basis2THF//ωB97XD/basis1gas‑phase level. For more extensive inves-
tigations with other density functionals (BP86, M06, M06-2X) and
computational details, see the Supporting Information.
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