DOI: 10.1126/science.287.5460.1992. Efficient Activation of Aromatic C-H Bonds for Addition to C-C Multiple Bonds

Efficient Activation of Aromatic C-H Bonds for Addition to C-C Multiple Bonds

10.1126/science.287.5460.1992

Crossref journal-article

American Association for the Advancement of Science (AAAS)

Science (221)

Abstract

Efficient electrophilic metalation of aromatic C–H bonds leading to new C–C bond formation through regio- and stereoselective addition to alkynes and alkenes has been realized by a catalytic amount (0.02 to 5 mole percent) of palladium(II) or platinum(II) compounds in a mixed solvent containing trifluoroacetic acid at room temperature. Various arenes undergo unexpected selective trans hydroarylation to terminal or internal C≡C bonds inter- and intramolecularly with high efficiency (up to a turnover number of 4500 for palladium), especially for electron-rich arenes, giving thermodynamically unfavorablecis-alkenes, and the oxygen- and nitrogen-containing heterocycles. The simplicity, generality, and efficiency of this process should be very attractive to the possible industrial application for the functionalization of arenes.

Bibliography

Jia, C., Piao, D., Oyamada, J., Lu, W., Kitamura, T., & Fujiwara, Y. (2000). Efficient Activation of Aromatic C-H Bonds for Addition to C-C Multiple Bonds. Science, 287(5460), 1992â1995.

Authors 6

Chengguo Jia (first)
Dongguo Piao (additional)
Juzo Oyamada (additional)
Wenjun Lu (additional)
Tsugio Kitamura (additional)
Yuzo Fujiwara (additional)

References 28 Referenced 791

E. Shilov and G. B. Shul'pin Chem. Rev. 97 2879 (1997). (10.1021/cr9411886)
S. Murai Ed. Activation of Unreactive Bonds and Organic Synthesis vol. 3 of Topics in Organometallic Chemistry (Springer-Verlag New York 1999). (10.1007/3-540-68525-1)
C. L. Hill Ed. Activation and Functionalization of Alkanes (Wiley New York 1989).
10.1038/366529a0
10.1021/ja990702s
10.1246/cl.1995.681
10.1246/cl.1980.507
10.1021/om00049a045
10.1016/S0040-4039(00)90648-8
10.1021/ja01053a047
10.1055/s-1996-5541
10.1021/ol991148u
S. Patai Ed. The Chemistry of Carbon-Carbon Triple Bonds (Wiley New York 1978).
J. Tsuji Palladium Reagents and Catalysts (Wiley New York 1995).
10.1039/p19740001289
10.1016/S0022-328X(00)87439-2
10.1021/jp9621944
10.1021/om00101a019
10.1021/jo9820059
D. Zargarrian and H. Alper Organometallics 12 712 (1993). (10.1021/om00027a022)
Two control reactions also support the formation of IMc in the reaction: (i) The D-containing adduct of reaction 1 in Fig. 4 cannot be formed from H/D exchange of the corresponding 1/1 arene/alkyne adduct in TFA- d 1 and (ii) the 1/2 arene/alkyne adduct as ArA 2 (in Fig. 2) cannot result from the reaction in TFA- d 1 or from the reaction of 1/1 arene/alkyne adduct with another alkyne. ArA 2 would be formed by cis addition of the vinyl-Pd complex IMc to the alkyne followed by protonation.
10.1021/om990179q
M–H or M–R trans additions across C–C triple bonds and Pd(II)-catalyzed inter- and intramolecular trans hydroacetoxylation of alkynes have been reported and in some cases trans additions are the preferred addition mode.
10.1021/om00038a011
10.1016/S0040-4039(00)60873-0
10.1021/ar980016i
10.1021/ja973926o
We thank the financial support from Monbusho [Scientific Research (A) grant 09355031] and research fellowship P98430 (to C.J.) from the Japan Society for the Promotion of Science.

Dates

Type	When
Created	23 years ago (July 27, 2002, 5:40 a.m.)
Deposited	8 months, 2 weeks ago (Dec. 8, 2024, 1:01 p.m.)
Indexed	3 weeks ago (Aug. 2, 2025, 12:50 a.m.)
Issued	25 years, 5 months ago (March 17, 2000)
Published	25 years, 5 months ago (March 17, 2000)
Published Print	25 years, 5 months ago (March 17, 2000)

Funders 0

None

BibTeX

@article{Jia_2000, title={Efficient Activation of Aromatic C-H Bonds for Addition to C-C Multiple Bonds}, volume={287}, ISSN={1095-9203}, url={http://dx.doi.org/10.1126/science.287.5460.1992}, DOI={10.1126/science.287.5460.1992}, number={5460}, journal={Science}, publisher={American Association for the Advancement of Science (AAAS)}, author={Jia, Chengguo and Piao, Dongguo and Oyamada, Juzo and Lu, Wenjun and Kitamura, Tsugio and Fujiwara, Yuzo}, year={2000}, month=mar, pages={1992–1995} }

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