ACS Catalysis
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terminal state C. The desired ketone compound is probably
(7) Fiorito, D.; Folliet, S.; Liu, Y.; Mazet, C. A general nickel-
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catalyzed Kumada vinylation for the preparation of 2-
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of ethers via C–O bond cleavage: a new strategy for molecu-
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produced upon hydrolysis in the work up procedure.
In summary, we have developed a Kumada arylation of
secondary amides for the synthesis of unsymmetrical aryl
ketones with cost-effective chromium catalysis. This reac-
tion was enabled by the use of low-cost chromium salt as
precatalyst combined with trimethylsilyl chloride as additive
to give ketone products upon work up. The ketone is proba-
bly protected in the reaction cycle, thereby without forming
the adduct of Grignard reagent to ketone. It presents a rare
example of the use of readily available secondary amides as
reactants for the arylative C–C bond formation reaction by
catalytic activation of benzimidate intermediate with chro-
mium at room temperature. Further studies on understand-
ing the mechanism and application of the Cr-catalyzed pro-
tocol in synthesis are under way.
(10) Tobisu, M.; Chatani, N. Cross-couplings using aryl ethers via
C–O bond activation enabled by nickel catalysts. Acc. Chem.
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(11) Heller, S. T.; Newton, J. N.; Fu, T.; Sarpong, R. One-pot un-
symmetrical ketone synthesis employing a pyrrole-bearing
formal carbonyl dication linchpin reagent. Angew. Chem., Int.
Ed. 2015, 54, 9839–9843.
(12) Cuquerella, M. C.; Lhiaubet-Vallet, V.; Cadet, J.; Miranda, M.
A. Benzophenone photosensitized DNA damage. Acc. Chem.
Res. 2012, 45, 1558–1570.
(13) McDaniel, R.; Thamchaipenet, A.; Gustafsson, C.; Fu, H.;
Betlach, M.; Betlach, M.; Ashley, G. Multiple genetic modifi-
cations of the erythromycin polyketide synthase to produce
a library of novel “unnatural” natural products. Proc. Natl.
Acad. Sci. USA 1999, 96, 1846–1851.
(14) Zhang, X.; MacMillan, D. W. C. Direct aldehyde C–H aryla-
tion and alkylation via the combination of nickel, hydrogen
atom transfer, and photoredox catalysis. J. Am. Chem. Soc.
2017, 139, 11353−11356.
ASSOCIATED CONTENT
Supporting Information. Experimental procedures, characteri-
zation data for all products, detailed optimized geometries, and
free energies. This material is available free of charge via the
AUTHOR INFORMATION
Corresponding Author
*E-mail: zengxiaoming@scu.edu.cn
(15) Vandavasi, J. K.; Hua, X. Halima, H. B.; Newman, S. G. A
nickel-catalyzed carbonyl-Heck reaction. Angew. Chem. Int.
Ed. 2017, 56,15441–15445.
Author Contributions
§C. Chen and P. Liu contributed equally.
(16) Kinney, R. G.; Tjutrins, J.; Torres, G. M.; Liu, N. J.; Kulkarni,
O.; Arndtsen, B. A. A general approach to intermolecular
carbonylation of arene C–H bonds to ketones through cata-
lytic aroyl triflate formation. Nat. Chem. 2018, 10, 193–199.
(17) (a) Bang, C. G.; Jensen, J. F.; O’Hanlon Cohrt, E.; Olsen, L. B.;
Siyum, S. G.; Mortensen, K. T.; Skovgaard, T.; Berthelsen, J.;
Yang, L.; Givskov, M.; Qvortrup, K.; Nielsen, T. E. A linker for
the solid-phase synthesis of hydroxamic acids and identifi-
cation of HDAC6 inhibitors. ACS Comb. Sci. 2017, 19, 657–
669. (b) Theodorou, V.; Skobridis, K.; Karkatsoulis, A. Base-
induced rearrangement of tritylamines to imines: Discovery
and investigation of the mechanism. Tetrahedron 2007, 63,
4284–4289.
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
We thank the National Natural Science Foundation of China
(Nos. 21202128, 21572175), XJTU and SCU for financial support
of this research.
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