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Journal of the American Chemical Society
hanced donor and acceptor properties. The high ambiphilic
1
2
3
4
5
6
7
8
character allows for intramolecular carbene insertion into an
unactivated C(sp3)-H bond. Since such a process does not
occur in the cases of 5a and 5b, it will not preclude the syn-
thetic availability of a wide variety of CAAC-6 derivatives.
Our results demonstrate the superiority of CAAC-6 over their
CAAC-5 counterparts in the α-arylation of ketones with aryl
chlorides. Other catalytic chemical transformations are under
current investigation, since it is safe to predict that the peculiar
electronic properties of CAAC-6 will result in very strong
metal-carbene bonds, which will allow for catalysis at high
temperatures. This novel family of carbenes should also be
useful for stabilizing electron-poor and paramagnetic species.
Chem. Res. 2016, 49, 357. (e) Paul, U. S. D.; Radius, U. Eur. J. Inorg.
Chem. 2017, 3362.
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3
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Carbenes : From Laboratory Curiosities to Efficient Synthetic Tools,
Royal Society of Chemistry: Cambridge, 2016; (d) Nolan, S. P. N-
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Wiley-VCH: Weinheim, 2014. (e) Droege, T.; Glorius, F. Angew.
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See for examples: (a) Anderson, D. R.; Lavallo, V.; O’leary, D. J.;
ASSOCIATED CONTENT
Supporting Information
Bertrand, G.; Grubbs, R. H. Angew. Chem. Int. Ed. 2007, 46, 7262.
(b) Marx, V. M.; Sullivan, A. H.; Melaimi, M.; Virgil, S. C.; Keitz, B.
K.; Weinberger, D. S.; Bertrand, G.; Grubbs, R. H. Angew. Chem. Int.
Ed. 2015, 54, 1919. (c) Lavallo, V.; Frey, G. D.; Donnadieu, B.;
Soleilhavoup, M.; Bertrand, G. Angew. Chem. Int. Ed. 2008, 47, 5224.
(d) Hu, X.; Soleilhavoup, M.; Melaimi, M.; Chu, J.; Bertrand, G.
Angew. Chem. Int. Ed. 2015, 54, 6008. (e) Jin, L.; Tolentino, D. R.;
Melaimi, M.; Bertrand, G. Sci. Adv. 2015, 1, e1500304. (f) Jin, L.;
Romero, E. A.; Melaimi, M.; Bertrand, G. J. Am. Chem. Soc. 2015,
137, 15696. (g) Romero, E. A.; Jazzar, R.; Bertrand, G. Chem. Sci.
2017, 8, 165. (h) Gawin, R.; Kozakiewicz, A.; Gunka, P. A.;
Dabrowski, P.; Skowerski, K. Angew. Chem. Int. Ed. 2017, 56, 981.
(i) Butilkov, D.; Frenklah, A.; Rozenberg, I.; Kozuch, S.; Lemcoff, N.
G. ACS Catal. 2017, 7, 7634. (j) Wei, Y.; Rao, B.; Cong, X.; Zeng, X.
J. Am. Chem. Soc. 2015, 137, 9250. (k) Wiesenfeldt, M. P.; Nairoukh,
Z.; Glorius, F. Science 2017, 357, 908.
The Supporting Information is available free of charge on the
ACS Publications website at DOI: xxxxxxxxxxxxxxxx
General methods and materials, experimental procedures and
characterization data, X-ray crystal structure determination, com-
putational
section,
and
NMR
spectra
(PDF)
Crystallographic data for 5c (CCDC 1580015), 6c (CCDC
1580016), 7c (CCDC 1580013), 10 (CCDC 1580014), 11 (CCDC
1845430), 12a (CCDC 1837571) (CIF).
AUTHOR INFORMATION
6
Corresponding Author
(a) Romanov, A. S.; Di, D.; Yang, L.; Fernandez-Cestau, J.;
Becker, C. R.; James, C. E.; Zhu, B.; Linnolahti, M.; Credington,
D.; Bochmanm, M. Chem. Commun. 2016, 52, 6379. (b) Geernert,
M.; Müller, U.; Haehnel, M.; Pflaum, J.; Steffen, A. Chem. Eur. J.
2017, 23, 2206. (c) Di. D.; Romanov, A. S.; Yang, L.; Richter, J.
M.; Rivett, J. P. H.; Jones, S.; Thomas, T. H.; Jalebi, M. A.;
Friend, R. H.; Linnolahti, M.; Bochmann, M.; Credginton, D.
Science 2017, 356, 159. (d) Hamze, R.; Jazzar, R.; Soleihavoup,
M.; Djurovich, P. I.; Bertrand, G.; Thompson, M. E. Chem. Com-
mun. 2017, 53, 9008.
*gbertrand@ucsd.edu
ORCID
Glen Junor: 0000-0002-6733-3577
Rodolphe Jazzar: 0000-0002-4156-7826
Mohand Melaimi: 0000-0003-3553-1381
Guy Bertrand: 0000-0003-2623-2363
Funding Sources
7
For reviews, see: (a) Martin, C. D.; Soleilhavoup, M.; Bertrand,
No competing financial interests have been declared.
G. Chem. Sci. 2013, 4, 3020. (b) Mondal, K. C.; Roy, S.; Roesky,
H. W. Chem. Soc. Rev. 2016, 45, 1080.
ACKNOWLEDGMENT
8 Munz, D.; Chu, J.; Melaimi, M.; Bertrand, G. Angew. Chem. Int.
Ed. 2016, 55, 12886. (b) Mahoney, J. K.; Martin, D.; Thomas, F.;
Moore, C. E.; Rheingold, A. L.; Bertrand, G. J. Am. Chem. Soc.
2015, 137, 7519. (c) Jin, L.; Melaimi, M.; Liu, L.; Bertrand, G.
Org. Chem. Front. 2014, 1, 351. (d) Li, Y.; Mondal, K. C.; Samu-
el, P. P.; Zhu, H.; Orben, C. M.; Panneerselvam, S.; Dittrich, B.;
Schwederski, B.; Kaim, W.; Mondal, T.; Koley, D.; Roesky, H.
W. Angew. Chem. Int. Ed. 2014, 53, 4168. (f) Mahoney, J. K.;
Martin, D.; Moore, C. E.; Rheingold, A. L.; Bertrand, G. J. Am.
Chem. Soc. 2013, 135, 18766. (g) Kretschmer, R.; Ruiz, D. A.;
Moore, C. E.; Rheingold, A. L.; Bertrand, G. Angew. Chem. Int.
Ed., 2014, 53, 8176. (h) Bissinger, P; Braunschweig, H.; Damme,
A.; Krummenacher, I.; Phukan. A. K.; Radacki, K.; Sugawara, S.
Angew. Chem. Int. Ed. 2014, 53, 7360. (i) Roy, S.; Stückl, A. C.;
Demeshko, S.; Dittrich, B.; Meyer, J.; Maity, B.; Koley, D.;
Schwederski, B.; Kaim, W.; Roesky, H. W. J. Am. Chem. Soc.
2015, 137, 4670. (j) Mondal, K. C.; Dittrich, B.; Maity, B.; Koley,
D.; Roesky, H. W. J. Am. Chem. Soc. 2014, 136, 9568. (k) Gu, L.;
Zheng, Y.; Haldón, E.; Goddard, R.; Bill, E.; Thiel, W.; Alcarazo,
M. Angew. Chem. Int. Ed. 2017, 56, 8790. (l) Mondal, K. C.;
Roesky, H. W.; Stückl, A. C.; Ihret, F.; Kaim, W.; Dittrich, B.;
This work was supported by the U.S. Department of Energy,
Office of Science, Basic Energy Sciences, Catalysis Science
Program, under Award # DE-SC0009376. Thanks are due to the
Alfred P. Sloan Foundation’s University Center for Exemplary
Mentoring (GPJ), and to the Keck Foundation for funding the
KeckII computer center. Dr. Milan Gembicky and Dr. Curtis E.
Moore are greatly acknowledged for their assistance in X-ray
crystallography.
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