scholarly journals Ni(I)-Alkyl Complexes Bearing Phenanthroline Ligands: Experimental Evidence for CO2 Insertion at Ni(I) Centers

2020 ◽  
Author(s):  
Rosie Somerville ◽  
Carlota Odena ◽  
Marc Obst ◽  
Nilay Hazari ◽  
Kathrin Hopmann ◽  
...  
Keyword(s):  
Experimental Evidence ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Alkyl Complexes ◽  
Cross Coupling Reactions ◽  
Species Complexes ◽  
Alkyl Electrophiles ◽  
Metal Catalyzed ◽  
Phenanthroline Ligands

ABSTRACT: Although the catalytic carboxylation of unactivated alkyl electrophiles has reached remarkable levels of sophistication, the intermediacy of (phenanthroline)Ni(I)-alkyl species – complexes proposed in numerous Ni-catalyzed reductive cross-coupling reactions – has been subject to speculation. Herein, we report the synthesis of such elusive (phenanthroline)Ni(I) species and their reactivity with CO2, allowing us to address a long-standing challenge related to metal-catalyzed carboxylation reactions. <div> </div>

scholarly journals Ni(I)-Alkyl Complexes Bearing Phenanthroline Ligands: Experimental Evidence for CO2 Insertion at Ni(I) Centers

2020 ◽  
Author(s):  
Rosie Somerville ◽  
Carlota Odena ◽  
Marc Obst ◽  
Nilay Hazari ◽  
Kathrin Hopmann ◽  
...  
Keyword(s):  
Experimental Evidence ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Alkyl Complexes ◽  
Cross Coupling Reactions ◽  
Species Complexes ◽  
Alkyl Electrophiles ◽  
Metal Catalyzed ◽  
Phenanthroline Ligands

ABSTRACT: Although the catalytic carboxylation of unactivated alkyl electrophiles has reached remarkable levels of sophistication, the intermediacy of (phenanthroline)Ni(I)-alkyl species – complexes proposed in numerous Ni-catalyzed reductive cross-coupling reactions – has been subject to speculation. Herein, we report the synthesis of such elusive (phenanthroline)Ni(I) species and their reactivity with CO2, allowing us to address a long-standing challenge related to metal-catalyzed carboxylation reactions. <div> </div>

Striving to exploit alkyl electrophiles: challenge and choice in transition metal-catalyzed cross-coupling reactions of sulfones

2018 ◽  
Vol 5 (17) ◽  
pp. 2615-2617 ◽  
Author(s):  
Mengli Liu ◽  
Yannan Zheng ◽  
Guanyinsheng Qiu ◽  
Jie Wu
Keyword(s):  
Transition Metal ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Radical Process ◽  
Cross Coupling Reactions ◽  
Alkyl Electrophiles ◽  
Transition Metal Catalyzed ◽  
Metal Catalyzed

Transition metal-catalyzed cross-coupling reactions of alkyl sulfones as crystalline and readily available alkyl electrophiles via a radical process are highlighted.

Monodentate Trialkylphosphines: Privileged Ligands in Metal-catalyzed Crosscoupling Reactions

2020 ◽  
Vol 24 (3) ◽  
pp. 231-264 ◽  
Author(s):  
Kevin H. Shaughnessy
Keyword(s):  
Transition Metal ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Aryl Bromides ◽  
Wide Range ◽  
Sterically Demanding ◽  
Transition Metal Catalyzed ◽  
Catalyzed Reactions ◽  
Metal Catalyzed

Phosphines are widely used ligands in transition metal-catalyzed reactions. Arylphosphines, such as triphenylphosphine, were among the first phosphines to show broad utility in catalysis. Beginning in the late 1990s, sterically demanding and electronrich trialkylphosphines began to receive attention as supporting ligands. These ligands were found to be particularly effective at promoting oxidative addition in cross-coupling of aryl halides. With electron-rich, sterically demanding ligands, such as tri-tertbutylphosphine, coupling of aryl bromides could be achieved at room temperature. More importantly, the less reactive, but more broadly available, aryl chlorides became accessible substrates. Tri-tert-butylphosphine has become a privileged ligand that has found application in a wide range of late transition-metal catalyzed coupling reactions. This success has led to the use of numerous monodentate trialkylphosphines in cross-coupling reactions. This review will discuss the general properties and features of monodentate trialkylphosphines and their application in cross-coupling reactions of C–X and C–H bonds.

Synthesis of Marine Polyacetylenes Callyberynes A−C by Transition-Metal-Catalyzed Cross-Coupling Reactions to sp Centers

2006 ◽  
Vol 71 (7) ◽  
pp. 2802-2810 ◽  
Author(s):  
Susana López ◽  
Francisco Fernández-Trillo ◽  
Pilar Midón ◽  
Luis Castedo ◽  
Carlos Saá
Keyword(s):  
Transition Metal ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Transition Metal Catalyzed ◽  
Metal Catalyzed

scholarly journals Protecting group-free, selective cross-coupling of alkyltrifluoroborates with borylated aryl bromides via photoredox/nickel dual catalysis

2015 ◽  
Vol 112 (39) ◽  
pp. 12026-12029 ◽  
Author(s):  
Yohei Yamashita ◽  
John C. Tellis ◽  
Gary A. Molander
Keyword(s):  
Small Molecules ◽  
Functional Group ◽  
Cross Coupling ◽  
Differential Protection ◽  
Coupling Reactions ◽  
Protecting Group ◽  
Cross Coupling Reactions ◽  
Aryl Bromides ◽  
Rapid Construction ◽  
Metal Catalyzed

Orthogonal reactivity modes offer substantial opportunities for rapid construction of complex small molecules. However, most strategies for imparting orthogonality to cross-coupling reactions rely on differential protection of reactive sites, greatly reducing both atom and step economies. Reported here is a strategy for orthogonal cross-coupling wherein a mechanistically distinct activation mode for transmetalation of sp3-hybridized organoboron reagents enables C-C bond formation in the presence of various protected and unprotected sp2-hybridized organoborons. This manifold has the potential for broad application, because orthogonality is inherent to the activation mode itself. The diversification potential of this platform is shown in the rapid elaboration of a trifunctional lynchpin through various transition metal-catalyzed processes without nonproductive deprotection or functional group manipulation steps.

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