TY - JOUR
T1 - Decarbonylative organoboron cross-coupling of esters by nickel catalysis
AU - Muto, Kei
AU - Yamaguchi, Junichiro
AU - Musaev, Djamaladdin G.
AU - Itami, Kenichiro
N1 - Funding Information:
This work was supported by the ERATO program from JST (K.I.), the Funding Program for Next Generation World-Leading Researchers from JSPS (220GR049 to K.I.), a Grant-in-Aid for Scientific Research on Innovative Areas ‘Molecular Activation Directed toward Straightforward Synthesis’ (25105720 to J.Y.) and KAKENHI (25708005 to J.Y.) from MEXT. The computational studies were supported by the National Science Foundation under the CCI Center for Selective C–H Functionalization (CHE-1205646). D.G.M. acknowledges NSF MRI-R2 grant (CHE-0958205) and the resources of the Cherry Emerson Center for Scientific Computation. K.M. thanks the Japan Society for the Promotion of Science (JSPS) for fellowships. Dr Lingkui Meng and Mr. Kazuma Amaike (Nagoya University) are acknowledged for their early studies. We thank Dr Ayako Miyazaki (Nagoya University), Prof. Cathleen M. Crudden (Queen’s University) and Dr Kei Murakami (Nagoya University) for fruitful discussion and critical comments. ITbM is supported by the World Premier International Research Center (WPI) Initiative, Japan.
PY - 2015/6/29
Y1 - 2015/6/29
N2 - The Suzuki-Miyaura cross-coupling is a metal-catalysed reaction in which boron-based nucleophiles and halide-based electrophiles are reacted to form a single molecule. This is one of the most reliable tools in synthetic chemistry, and is extensively used in the synthesis of pharmaceuticals, agrochemicals and organic materials. Herein, we report a significant advance in the choice of electrophilic coupling partner in this reaction. With a user-friendly and inexpensive nickel catalyst, a range of phenyl esters of aromatic, heteroaromatic and aliphatic carboxylic acids react with boronic acids in a decarbonylative manner. Overall, phenyl ester moieties function as leaving groups. Theoretical calculations uncovered key mechanistic features of this unusual decarbonylative coupling. Since extraordinary numbers of ester-containing molecules are available both commercially and synthetically, this new a € estera € cross-coupling should find significant use in synthetic chemistry as an alternative to the standard halide-based Suzuki-Miyaura coupling.
AB - The Suzuki-Miyaura cross-coupling is a metal-catalysed reaction in which boron-based nucleophiles and halide-based electrophiles are reacted to form a single molecule. This is one of the most reliable tools in synthetic chemistry, and is extensively used in the synthesis of pharmaceuticals, agrochemicals and organic materials. Herein, we report a significant advance in the choice of electrophilic coupling partner in this reaction. With a user-friendly and inexpensive nickel catalyst, a range of phenyl esters of aromatic, heteroaromatic and aliphatic carboxylic acids react with boronic acids in a decarbonylative manner. Overall, phenyl ester moieties function as leaving groups. Theoretical calculations uncovered key mechanistic features of this unusual decarbonylative coupling. Since extraordinary numbers of ester-containing molecules are available both commercially and synthetically, this new a € estera € cross-coupling should find significant use in synthetic chemistry as an alternative to the standard halide-based Suzuki-Miyaura coupling.
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U2 - 10.1038/ncomms8508
DO - 10.1038/ncomms8508
M3 - Article
AN - SCOPUS:84934325537
SN - 2041-1723
VL - 6
JO - Nature Communications
JF - Nature Communications
M1 - 7508
ER -