Organic Letters
Letter
nickel(0) generates a Ni(I) species D that is the active catalyst
for the Suzuki−Miyaura type C−C bond-forming reaction
(Scheme 4). The oxidative addition of the aryl iodide to the
nickel (0) species C, followed by transmetalation and reductive
elimination, generates the desired C−N coupling product 4.
The bulky ate complex facilitates reductive elimination (see the
catalyst recovered from the Buchwald−Hartwig type amination
the Suzuki−Miyaura type reaction starts with a transmetalation
step, which is followed by oxidative addition and reductive
elimination to generate 5, which completes the catalytic cycle
after the reaction has the same structure as intermediate B (see
only a base but also the support for the nickel catalyst.
In summary, we demonstrated activator-promoted aryl
halide-dependent chemoselective Buchwald−Hartwig and
Suzuki−Miyaura type reactions using nickel iodide under
similar conditions. This finding will help to develop new
selective reaction modes that are different from well-
established classical modes. We are currently developing
other selective catalytic systems on the basis of our new
findings.
Daisuke Hashizume − RIKEN Center for Emergent Matter
Hikaru Takaya − Institute for Chemical Research, Kyoto
Complete contact information is available at:
Author Contributions
∇R.N.D. and A.S. contributed equally.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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We thank Dr. Tetsuo Honma (JASRI, Spring-8) for assistance
with the XAFS studies (Spring-8, BL14B2). We are grateful for
the Materials Characterization Support Unit, RIKEN Center
for Emergent Matter Science for elemental analysis, and Ms.
Aya Ohno (RIKEN Center for Sustainable Resource Science)
for the assistance with ICP-MS. We gratefully acknowledge
financial support from the JST ACT-C (#JPMJCR12ZC), the
JST ACCEL (#JPMJAC1401), the JSPS (#24550126,
#20655035, and #15K05510), AMED (#19ak0101115h), the
Takeda Science Foundation, the Naito Foundation, and
RIKEN.
ASSOCIATED CONTENT
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* Supporting Information
The Supporting Information is available free of charge at
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General information, experimental procedures, coupling
data, ICP-MS analysis, NMR and XAFS experiments,
crystal structure data, and characterization data (PDF)
Accession Codes
CCDC 1950351 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION
Corresponding Authors
■
Yoichi M. A. Yamada − RIKEN Center for Sustainable Resource
Yasuhiro Uozumi − RIKEN Center for Sustainable Resource
Science, Wako, Saitama 351-0198, Japan; Institute for
Molecular Science, Okazaki, Aichi 444-8787, Japan;
Authors
Raghu N. Dhital − RIKEN Center for Sustainable Resource
Science, Wako, Saitama 351-0198, Japan
Abhijit Sen − RIKEN Center for Sustainable Resource Science,
Wako, Saitama 351-0198, Japan
Takuma Sato − RIKEN Center for Sustainable Resource Science,
Wako, Saitama 351-0198, Japan
Hao Hu − RIKEN Center for Sustainable Resource Science,
Wako, Saitama 351-0198, Japan
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R.; Belderrain, T. R.; Nicasio, M. C. ACS Catal. 2018, 8, 3733.
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(b) Zultanski, S. L.; Fu, G. C. J. Am. Chem. Soc. 2013, 135, 624.
Rikako Ishii − RIKEN Center for Sustainable Resource Science,
Wako, Saitama 351-0198, Japan
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