Scalable Continuous Synthesis of Organozinc Reagents and Their Immediate Subsequent Coupling Reactions

2020 ◽  
Author(s):  
Gabriele Menges-Flanagan ◽  
Eva Deitmann ◽  
Lars Gössl ◽  
Christian Hofmann ◽  
Patrick Löb
Keyword(s):  
Coupling Reactions ◽  
Continuous Synthesis ◽  
Organozinc Reagents

Lewis Acid-Promoted Coupling Reactions of Acid Chlorides with Organoaluminum and Organozinc Reagents

1997 ◽  
Vol 62 (13) ◽  
pp. 4327-4329 ◽  
Author(s):  
Mitsuhiro Arisawa ◽  
Yasuhiro Torisawa ◽  
Michiaki Kawahara ◽  
Masamichi Yamanaka ◽  
Atsushi Nishida ◽  
...  
Keyword(s):  
Lewis Acid ◽  
Coupling Reactions ◽  
Acid Chlorides ◽  
Organozinc Reagents

scholarly journals Ni-Catalyzed Electrochemical C(sp2)−C(sp3) Cross-Coupling Reactions

2020 ◽  
Author(s):  
Jian Luo ◽  
Bo Hu ◽  
wenda wu ◽  
maowei hu ◽  
Tianbiao Liu
Keyword(s):  
Aryl Halide ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Ambient Conditions ◽  
Acid Modification ◽  
Cross Coupling Reactions ◽  
Cross Coupling Reaction ◽  
Organozinc Reagents ◽  
Industrial Adoption

Nickel (Ni) catalyzed carbon-carbon (C−C) cross-coupling has been considerably developed in last decades and has demonstrated unique reactivities compared to palladium. However, existing Ni catalyzed cross-coupling reactions, despite success in organic synthesis, are still subject to the use of air-sensitive nucleophiles (i.e. Grignard and organozinc reagents), or catalysts (i.e. Ni<sup>0</sup> pre-catalysts), significantly limiting their academic and industrial adoption. Herein, we report that, through electrochemical voltammetry screening and optimization, the redox neutral C(sp<sup>2</sup>)‒C(sp<sup>3</sup>) cross-coupling can be accomplished in an undivided cell configuration using bench-stable aryl halide or β-bromostyrene (electrophiles) and benzylic trifluoroborate (nucleophiles) reactants, non-precious, bench stable catalysts consisting of NiCl<sub>2</sub>•glyme pre-catalyst and polypyridine ligands under ambient conditions. The broad reaction scope and good yields of the Ni-catalyzed electrochemical coupling reaction were confirmed by 48 examples of aryl/β-styrenyl chloride/bromide and benzylic trifluoroborates. Its potential applications were demonstrated by late-stage functionalization of pharmaceuticals and natural amino acid modification. Furthermore, this electrochemical C−C cross-coupling reaction was demonstrated at gram-scale in a flow-cell electrolyzer for practical industrial adoption. Finally, an array of chemical and electrochemical studies mechanistically indicates that electrochemical C−C cross-coupling reaction proceeds through an unconventional radical trans-metalation mechanism.

scholarly journals Ni-Catalyzed Electrochemical C(sp2)−C(sp3) Cross-Coupling Reactions

2020 ◽  
Author(s):  
Jian Luo ◽  
Bo Hu ◽  
wenda wu ◽  
maowei hu ◽  
Tianbiao Liu
Keyword(s):  
Aryl Halide ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Ambient Conditions ◽  
Acid Modification ◽  
Cross Coupling Reactions ◽  
Cross Coupling Reaction ◽  
Organozinc Reagents ◽  
Industrial Adoption

Nickel (Ni) catalyzed carbon-carbon (C−C) cross-coupling has been considerably developed in last decades and has demonstrated unique reactivities compared to palladium. However, existing Ni catalyzed cross-coupling reactions, despite success in organic synthesis, are still subject to the use of air-sensitive nucleophiles (i.e. Grignard and organozinc reagents), or catalysts (i.e. Ni<sup>0</sup> pre-catalysts), significantly limiting their academic and industrial adoption. Herein, we report that, through electrochemical voltammetry screening and optimization, the redox neutral C(sp<sup>2</sup>)‒C(sp<sup>3</sup>) cross-coupling can be accomplished in an undivided cell configuration using bench-stable aryl halide or β-bromostyrene (electrophiles) and benzylic trifluoroborate (nucleophiles) reactants, non-precious, bench stable catalysts consisting of NiCl<sub>2</sub>•glyme pre-catalyst and polypyridine ligands under ambient conditions. The broad reaction scope and good yields of the Ni-catalyzed electrochemical coupling reaction were confirmed by 48 examples of aryl/β-styrenyl chloride/bromide and benzylic trifluoroborates. Its potential applications were demonstrated by late-stage functionalization of pharmaceuticals and natural amino acid modification. Furthermore, this electrochemical C−C cross-coupling reaction was demonstrated at gram-scale in a flow-cell electrolyzer for practical industrial adoption. Finally, an array of chemical and electrochemical studies mechanistically indicates that electrochemical C−C cross-coupling reaction proceeds through an unconventional radical trans-metalation mechanism.

ChemInform Abstract: Lewis Acid Promoted Coupling Reactions of Acid Chlorides with Organoaluminum and Organozinc Reagents.

ChemInform ◽  
2010 ◽  
Vol 28 (45) ◽  
pp. no-no
Author(s):  
M. ARISAWA ◽  
Y. TORISAWA ◽  
M. KAWAHARA ◽  
M. YAMANAKA ◽  
A. NISHIDA ◽  
...  
Keyword(s):  
Lewis Acid ◽  
Coupling Reactions ◽  
Acid Chlorides ◽  
Organozinc Reagents

ChemInform Abstract: Negishi Cross-Coupling Reactions of α-Amino Acid-Derived Organozinc Reagents and Aromatic Bromides.

ChemInform ◽  
2008 ◽  
Vol 39 (24) ◽  
Author(s):  
Claire L. Oswald ◽  
Tomas Carrillo-Marquez ◽  
Lorenzo Caggiano ◽  
Richard F. W. Jackson
Keyword(s):  
Amino Acid ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Organozinc Reagents
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