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ACS Catalysis
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Camille and Henry-Dreyfus Foundation Teacher Scholar. We are grateful to Dr. Paul Anastas’ group
for use of their GC instrument, Dr. Brandon Mercado for assistance with X-ray crystallography,
Professor Mark Johnson and Dr. Fabian Menges for acquiring mass spectra and Louise Guard for
valuable discussions.
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Supporting information available
Characterizing data, further experimental details, X-ray information for 2b-IPr, 2c-IPr, 2d-IPr and 3,
References
1. (a) Hartwig, J. F. Acc. Chem. Res. 2008, 41, 1534-1544; (b) Marion, N.; Nolan, S. P. Acc. Chem. Res. 2008, 41, 1440-
1449; (c) Fu, G. C. Acc. Chem. Res. 2008, 41, 1555-1564; (d) Würtz, S.; Glorius, F. Acc. Chem. Res. 2008, 41, 1523-1533;
(e) Martin, R.; Buchwald, S. L. Acc. Chem. Res. 2008, 41, 1461-1473; (f) Johansson Seechurn, C. C. C.; Kitching, M. O.;
Colacot, T. J.; Snieckus, V. Angew. Chem. Int. Ed. 2012, 51, 5062-5085; (g) Li, H.; Johansson Seechurn, C. C. C.; Colacot,
T. J. ACS Catal. 2012, 2, 1147-1164; (h) Valente, C.; Calimsiz, S.; Hoi, K. H.; Mallik, D.; Sayah, M.; Organ, M. G. Angew.
Chem. Int. Ed. 2012, 51, 3314-3332.
2. (a) Littke, A. F.; Fu, G. C. Angew. Chem. Int. Ed. 1999, 38, 2411-2413; (b) Littke, A. F.; Dai, C.; Fu, G. C. J. Am. Chem.
Soc. 2000, 122, 4020-4028; (c) Wolfe, J. P.; Singer, R. A.; Yang, B. H.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121,
9550-9561; (d) Aranyos, A.; Old, D. W.; Kiyomori, A.; Wolfe, J. P.; Sadighi, J. P.; Buchwald, S. L. J. Am. Chem. Soc.
1999, 121, 4369-4378; (e) Wolfe, J. P.; Buchwald, S. L. Angew. Chem. Int. Ed. 1999, 38, 2413-2416; (f) Shelby, Q.;
Kataoka, N.; Mann, G.; Hartwig, J. J. Am. Chem. Soc. 2000, 122, 10718-10719; (g) Kataoka, N.; Shelby, Q.; Stambuli, J.
P.; Hartwig, J. F. J. Org. Chem. 2002, 67, 5553-5566; (h) Lundgren, R. J.; Hesp, K. D.; Stradiotto, M. Synlett 2011, 2443-
2458; (i) Lundgren, R. J.; Stradiotto, M. Chem. Eur. J. 2012, 18, 9758-9769.
3. Christmann, U.; Vilar, R. Angew. Chem. Int. Ed. 2005, 44, 366-374.
4. (a) Biscoe, M. R.; Fors, B. P.; Buchwald, S. L. J. Am. Chem. Soc. 2008, 130, 6686-6687; (b) Kinzel, T.; Zhang, Y.;
Buchwald, S. L. J. Am. Chem. Soc. 2010, 132, 14073-14075; (c) Bruno, N. C.; Tudge, M. T.; Buchwald, S. L. Chem. Sci.
2013, 4, 916-920.
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.; Chass, G. A.; Fang, D.-C.; Hopkinson, A. C.; Valente, C. Synthesis
2008, 2776-2797; (c) 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.
6. (a) Viciu, M. S.; Germaneau, R. F.; Nolan, S. P. Org. Lett. 2002, 4, 4053-4056; (b) Viciu, M. S.; Germaneau, R. F.;
Navarro-Fernandez, O.; Stevens, E. D.; Nolan, S. P. Organometallics 2002, 21, 5470-5472; (c) Navarro, O.; Kaur, H.;
Mahjoor, P.; Nolan, S. P. J. Org. Chem. 2004, 69, 3173-3180; (d) Marion, N.; Navarro, O.; Mei, J.; Stevens, E. D.; Scott,
N. M.; Nolan, S. P. J. Am. Chem. Soc. 2006, 128, 4101-4111.
7. (a) Hruszkewycz, D. P.; Balcells, D.; Guard, L. M.; Hazari, N.; Tilset, M. J. Am. Chem. Soc. 2014, 136, 7300-7316; (b)
Hruszkewycz, D. P.; Balcells, D.; Guard, L. M.; Hazari, N.; Feldman, N. Organometallics 2015, 34, 381-394.
8. For example the dimeric precursor 1d is available with product number 46-0868, while 2d-IPr is available with product
number 46-0815.
9. R. H. Crabtree, The Organometallic Chemistry of the Transition Metals. 6th ed.; Wiley, New York, 2014.
10. (a) Hüttel, R.; Kratzer, J. Angew. Chem. 1959, 71, 456; (b) Volger, H. C. Rec. Trav. Chim. Pays-Bas 1969, 88, 225-240;
(c) Hüttel, R. Synthesis 1970, 225-255; (d) Trost, B. M. Tetrahedron 1977, 33, 2615-2649; (e) Trost, B. M.; Strege, P. E.;
Weber, L.; Fullerton, T. J.; Dietsche, T. J. J. Am. Chem. Soc. 1978, 100, 3407-3415; (f) Liu, G.; Wu, Y. Top. Curr. Chem.
2010, 292, 195-209.
11. Bielinski, E. A.; Dai, W.; Guard, L. M.; Hazari, N.; Takase, M. K. Organometallics 2013, 32, 4025-4037.
12. Using this solvent mixture the reactions are homogeneous, which assists in accurate comparison of the precatalysts. We
also performed some catalytic reactions under the heterogeneous conditions that had been optimized for Cin-IPr by Nolan
and co-workers6d (see ESI).
13. (a) Tanase, T.; Nomura, T.; Yamamoto, Y.; Kobayashi, K. J. Organomet. Chem. 1991, 410, C25-C28; (b) Tanase, T.;
Nomura, T.; Fukushima, T.; Yamamoto, Y.; Kobayashi, K. Inorg. Chem. 1993, 32, 4578-4584; (c) Sui-Seng, C.; Enright,
G. D.; Zargarian, D. J. Am. Chem. Soc. 2006, 128, 6508-6519; (d) Dai, W.; Chalkley, M. J.; Brudvig, G. W.; Hazari, N.;
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