Transition‐Metal‐Free Cross‐Coupling by Using Tertiary Benzylic Organoboronates

Regiodivergent addition reactions provide straightforward and atom‐economic approaches to access different regioisomers. However, the regio‐chemistry control to access all the possible results is still challenging especially for the reaction involving multiple addition steps. Herein, we reported regio‐controllable cobalt‐catalyzed sequential hydrosilylation/hydroboration of arylacetylenes, delivering all the possible regio‐outcomes with high regioselectivities (up to >20/1 rr for all the cases). Each regioisomer of value‐added silylboronates could be efficiently and regioselectively obtained from the same materials. The adjustment of the ligands of cobalt catalysts combined with dual catalysis relay strategy is the key to achieve regio‐chemistry control. This regio‐controllable research might inspire the exploration of the diversity‐oriented synthesis that involves multiple additions and provide full sets of regioisomers of other synthetic useful molecules.

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Regio‐controllable Cobalt‐Catalyzed Sequential Hydrosilylation/Hydroboration of Arylacetylenes

Cheng

Guo

Sun

et al. 2021

Angewandte Chemie

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The Formal Cross‐Coupling of Amines and Carboxylic Acids to Form sp³–sp³ Carbon–Carbon Bonds

Zhang

Cernak

2021

Angewandte Chemie

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We have developed a deaminative–decarboxylative protocol to form new carbon(sp3)–carbon(sp3) bonds from activated amines and carboxylic acids. Amines and carboxylic acids are ubiquitous building blocks, available in broad chemical diversity and at lower cost than typical C−C coupling partners. To leverage amines and acids for C−C coupling, we developed a reductive nickel‐catalyzed cross‐coupling utilizing building block activation as pyridinium salts and redox‐active esters, respectively. Miniaturized high‐throughput experimentation studies were critical to our reaction optimization, with subtle experimental changes such as order of reagent addition, composition of a binary solvent system, and ligand identity having a significant impact on reaction performance. The developed protocol is used in the late‐stage diversification of pharmaceuticals while more than one thousand systematically captured and machine‐readable reaction datapoints are reposited.

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Regio‐controllable Cobalt‐Catalyzed Sequential Hydrosilylation/Hydroboration of Arylacetylenes

et al. 2021

View full text Add to dashboard Cite

Regiodivergent addition reactions provides traightforwarda nd atom-economic approaches to access different regioisomers.H owever,t he regio-chemistry control to access all the possible results is still challenging especially for the reaction involving multiple addition steps.Herein, we reported regio-controllable cobalt-catalyzed sequential hydrosilylation/ hydroboration of arylacetylenes,d elivering all the possible regio-outcomes with high regioselectivities (up to > 20/1 rr for all the cases). Each regioisomer of value-added silylboronates could be efficiently and regioselectively obtained from the same materials.T he adjustment of the ligands of cobalt catalysts combined with dual catalysis relays trategy is the key to achieve regio-chemistry control. This regio-controllable researchmight inspire the exploration of the diversity-oriented synthesis that involves multiple additions and provide full sets of regioisomers of other synthetic useful molecules.Scheme 1. Metal-catalyzed sequential hydrosilylation/hydroboration of arylacetylenes.

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Transition‐Metal‐Free Cross‐Coupling by Using Tertiary Benzylic Organoboronates

Cited by 5 publications

References 57 publications

Regio‐controllable Cobalt‐Catalyzed Sequential Hydrosilylation/Hydroboration of Arylacetylenes

Regio‐controllable Cobalt‐Catalyzed Sequential Hydrosilylation/Hydroboration of Arylacetylenes

The Formal Cross‐Coupling of Amines and Carboxylic Acids to Form sp³–sp³ Carbon–Carbon Bonds

Regio‐controllable Cobalt‐Catalyzed Sequential Hydrosilylation/Hydroboration of Arylacetylenes

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Transition‐Metal‐Free Cross‐Coupling by Using Tertiary Benzylic Organoboronates

Cited by 5 publications

References 57 publications

Regio‐controllable Cobalt‐Catalyzed Sequential Hydrosilylation/Hydroboration of Arylacetylenes

Regio‐controllable Cobalt‐Catalyzed Sequential Hydrosilylation/Hydroboration of Arylacetylenes

The Formal Cross‐Coupling of Amines and Carboxylic Acids to Form sp3–sp3 Carbon–Carbon Bonds

Regio‐controllable Cobalt‐Catalyzed Sequential Hydrosilylation/Hydroboration of Arylacetylenes

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Product

Resources

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The Formal Cross‐Coupling of Amines and Carboxylic Acids to Form sp³–sp³ Carbon–Carbon Bonds