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Mechanistic Investigation of Ni-Catalyzed Reductive Cross-Coupling of Alkenyl and Benzyl Electrophiles.
Turro, Raymond F; Wahlman, Julie L H; Tong, Z Jaron; Chen, Xiahe; Yang, Miao; Chen, Emily P; Hong, Xin; Hadt, Ryan G; Houk, K N; Yang, Yun-Fang; Reisman, Sarah E.
Afiliação
  • Turro RF; The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
  • Wahlman JLH; The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
  • Tong ZJ; The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
  • Chen X; College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, Zhejiang 310014, China.
  • Yang M; College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, Zhejiang 310014, China.
  • Chen EP; The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
  • Hong X; Department of Chemistry, Zhejiang University, Hangzhou, Zhejiang 310027, China.
  • Hadt RG; Arthur Amos Noyes Laboratory of Chemical Physics, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
  • Houk KN; Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States.
  • Yang YF; College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, Zhejiang 310014, China.
  • Reisman SE; The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
J Am Chem Soc ; 145(27): 14705-14715, 2023 Jul 12.
Article em En | MEDLINE | ID: mdl-37358565
Mechanistic investigations of the Ni-catalyzed asymmetric reductive alkenylation of N-hydroxyphthalimide (NHP) esters and benzylic chlorides are reported. Investigations of the redox properties of the Ni-bis(oxazoline) catalyst, the reaction kinetics, and mode of electrophile activation show divergent mechanisms for these two related transformations. Notably, the mechanism of C(sp3) activation changes from a Ni-mediated process when benzyl chlorides and Mn0 are used to a reductant-mediated process that is gated by a Lewis acid when NHP esters and tetrakis(dimethylamino)ethylene is used. Kinetic experiments show that changing the identity of the Lewis acid can be used to tune the rate of NHP ester reduction. Spectroscopic studies support a NiII-alkenyl oxidative addition complex as the catalyst resting state. DFT calculations suggest an enantiodetermining radical capture step and elucidate the origin of enantioinduction for this Ni-BOX catalyst.
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Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2023 Tipo de documento: Article País de afiliação: Estados Unidos
Texto completo
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XML
PubMed Links
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Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2023 Tipo de documento: Article País de afiliação: Estados Unidos