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Figure 1. A proposed mechanism of the dealkenylative alkenyl-
ation with styrene (2a).
In summary, we developed a novel, catalytic functionaliza-
tion of styrene derivatives via C–C bond cleavage. A variety of
alkenes including styrenes, unactivated aliphatic alkenes, and
allyl alcohols were applicable to the dealkenylative functional-
ization as coupling partners under the simple catalyst system.
This is the first example for conversion of the alkenyl groups in
styrene derivatives to various carbon functional groups. We
also revealed that the C–C bond was cleaved via hydromet-
alation followed by β-carbon elimination, and we believe that
this strategy can lead to development of new catalytic, more
challenging C–C bond functionalization reactions.
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website.
Full experimental details and characterization data (PDF)
AUTHOR INFORMATION
Corresponding Author
*kakiuchi@chem.keio.ac.jp
Notes
The authors declare no competing financial interest.
(3) For examples of catalytic, unstrained nonpolar C–C bond ac-
tivation through organometallic intermediate: (a) Liou, S.-Y.; van
der Boom, M.; Milstein, D. Catalytic Selective Cleavage of a Strong
C–C Single Bond by Rhodium in Solution. Chem. Commun. 1998,
687-688. (b) Mukai, C.; Ohta, Y.; Oura, Y.; Kawaguchi, Y.; Inagaki, F.
ACKNOWLEDGMENT
This work was supported in part by JSPS KAKENHI Grant Num-
bers JP17K19126 and JP15H05839 (Middle Molecular Strat-
egy). T.K. is also grateful for support by JSPS KAKENHI Grant
Numbers JP16H01040 and JP18H04271 (Precisely Designed
Catalysts with Customized Scaffolding). S.O. is also grateful for
support by JSPS Grant-in-Aid for JSPS Fellows Grant Number
JP19J13174.
3
Csp3–Csp and Csp3–H Bond Activation of 1,1-Disubstituted Cyclo-
pentane. J. Am. Chem. Soc. 2012, 134, 19580-19583. (c) Zhu, J.;
Wang, J.; Dong, G. Catalytic Activation of Unstrained C(aryl)–
C(aryl) Bonds in 2,2’-Biphenols. Nat. Chem. 2019, 11, 45-51. (d)
Zhu, J.; Chen, P.; Lu, G.; Liu, P.; Dong, G. Ruthenium-Catalyzed Re-
ductive Cleavage of Unstrained Aryl–Aryl Bonds: Reaction Devel-
opment and Mechanistic Study. J. Am. Chem. Soc. 2019, 141, 18630-
18640.
(4) Onodera, S.; Ishikawa, S. Kochi, T.; Kakiuchi, F. Direct
Alkenylation of Allylbenzenes via Chelation-Assisted C–C Bond
Cleavage. J. Am. Chem. Soc. 2018, 140, 9788-9792.
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