A5078657083- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Catalytic C–H Functionalization Methods
- Catalytic Cross-Coupling Reactions
- Synthetic Organic Chemistry Methods
- Asymmetric Hydrogenation and Catalysis
- Radical Photochemical Reactions
- Crystallography and molecular interactions
- CO2 Reduction Techniques and Catalysts
- Organometallic Complex Synthesis and Catalysis
- Organoboron and organosilicon chemistry
- Electrochemical Analysis and Applications
- Cyclopropane Reaction Mechanisms
- Asymmetric Synthesis and Catalysis
- Catalytic Alkyne Reactions
- Oxidative Organic Chemistry Reactions
- Advanced Nanomaterials in Catalysis
- Metal complexes synthesis and properties
- Porphyrin and Phthalocyanine Chemistry
- Polyoxometalates: Synthesis and Applications
- Synthesis and Catalytic Reactions
- Carbon dioxide utilization in catalysis
- Sulfur-Based Synthesis Techniques
- Advanced Chemical Sensor Technologies
Scripps Research Institute
2021-2024
Institut de Chimie et Biochimie Moléculaires et Supramoléculaires
2023-2024
Centre National de la Recherche Scientifique
2023-2024
Université Claude Bernard Lyon 1
2023-2024
Torrey Pines Institute For Molecular Studies
2024
Scripps (United States)
2024
Scripps Institution of Oceanography
2024
University of California, Berkeley
2019-2020
Herein we disclose a strategy to promote the hydrocarboxylation of unactivated alkenes using photochemical activation formate salts. We illustrate that an alternative initiation mechanism circumvents limitations prior approaches and enables this challenging substrate class. Specifically, found accessing requisite thiyl radical initiator without exogenous chromophore eliminates major byproducts have plagued attempts exploit similar reactivity for alkene substrates. This redox-neutral method...
An asymmetric 1,2-dicarbofunctionalization of unactivated alkenes with aryl iodides and aryl/alkenylboronic esters under nickel/bioxazoline catalysis is disclosed. A wide array alkenyl nucleophiles are tolerated, furnishing the products in good yield high enantioselectivity. In addition to terminal alkenes, 1,2-disubstituted internal participate reaction, establishing two contiguous stereocenters diastereoselectivity moderate combination experimental computational techniques shed light on...
Abstract Because internal alkenes are more challenging synthetic targets than terminal alkenes, metal‐catalyzed olefin mono‐transposition (i.e., positional isomerization) approaches have emerged to afford valuable E ‐ or Z‐ from their complementary alkene feedstocks. However, the applicability of these methods has been hampered by lack generality, commercial availability precatalysts, and scalability. Here, we report a nickel‐catalyzed platform for stereodivergent / Z ‐selective synthesis at...
Abstract There is a pressing need, particularly in the field of drug discovery, for general methods that will enable direct coupling tertiary alkyl fragments to (hetero)aryl halides. Herein uniquely powerful and simple set conditions achieving this transformation with unparalleled generality chemoselectivity disclosed. This new protocol placed context other recently reported methods, applied simplify routes known bioactive building blocks molecules, scaled up both batch flow. The role...
A flurry of recent research has centered on harnessing the power nickel catalysis in organic synthesis. These efforts have been bolstered by contemporaneous development well-defined (pre)catalysts with diverse structure and reactivity. In this report, we present ten different bench-stable, 18-electron, formally zero-valent nickel-olefin complexes that are competent pre-catalysts various reactions. Our investigation includes preparations novel, bench-stable Ni(COD)(L)...
ConspectusDue to the rarity of precious metals like palladium, nickel catalysis is becoming an increasingly important player in organic synthesis, especially for formation bonds with sp3-hybridized carbon centers. Traditionally, catalytic processes involving active Ni(0) species have relied on Ni(COD)2 or situ reduction Ni(II) salts. However, air- and temperature-sensitive material that requires use inert-atmosphere glovebox, protocols salts using metallic organometallic reductants add...
The steric effects of substituents on five-membered rings are less pronounced than those six-membered because the difference in bond angles. Thus, regioselectivities reactions heteroarenes that occur with selectivities dictated by effects, such as borylation C-H bonds, have been poor many cases. We report silylation five-membered-ring occurs high sterically derived regioselectivity when catalyzed combination [Ir(cod)(OMe)]
Abstract There is a pressing need, particularly in the field of drug discovery, for general methods that will enable direct coupling tertiary alkyl fragments to (hetero)aryl halides. Herein uniquely powerful and simple set conditions achieving this transformation with unparalleled generality chemoselectivity disclosed. This new protocol placed context other recently reported methods, applied simplify routes known bioactive building blocks molecules, scaled up both batch flow. The role...
The steric effects of substituents on five-membered rings are less pronounced than those six-membered because the difference in bond angles. Thus, regioselectivities reactions that occur with selectivities dictated by effects, such as borylation C-H bonds, have been poor many cases. We report silylation ring heteroarenes occurs high sterically derived regioselectivity when catalyzed combination [Ir(cod)(OMe)]
Abstract Over the last fifty years, use of nickel catalysts for facilitating organic transformations has skyrocketed. Nickel(0) sources act as useful precatalysts because they can enter a catalytic cycle through ligand exchange, without needing to undergo additional elementary steps. However, most Ni(0) are synthesized with stoichiometric aluminum–hydride reductants, pyrophoric reagents that not atom‐economical and must be used at cryogenic temperatures. Here, we demonstrate Ni(II) salts...
Because internal alkenes are more challenging synthetic targets than terminal alkenes, metal-catalyzed olefin trans-position (i.e., positional isomerization) approaches have emerged to afford valuable E- or Z- from their complementary alkene feedstocks. However, the applicability of these methods has been hampered by lack generality, commercial availability, and scalability. In this Communication, we report a nickel-catalyzed plat-form for stereodivergent Z-selective synthesis at room...
A flurry of recent research has centered on harnessing the power nickel catalysis in organic synthesis. These efforts have been bolstered by contemporaneous synthesis, characterization, and optimization well-defined (pre)catalysts with diverse structure reactivity. In this report, we present development ten different bench-stable, 18-electron, formally zero-valent nickel–olefin complexes that are shown to be competent pre-catalysts various reactions. Our investigation includes preparations...
There is a pressing need, particularly in the field of drug discovery, for general methods that will enable direct coupling tertiary alkyl frag-ments to (hetero)aryl halides. Herein uniquely powerful and simple set conditions achieving this transformation with unparalleled generality chemoselectivity disclosed. This new protocol placed context other recently reported methods, applied simplify routes known bioactive building blocks molecules, scaled up both batch flow. The role pyridine...
Achieving regio- and stereoselective formation of products from simple chemical building blocks is one the most important roles catalysis in organic synthesis. Repositioning an alkene functional group through catalytic isomerization represents a powerful synthetic strategy for preparing valuable comparatively feedstocks. The utility this approach, however, hinges on ability to control positional stereoisomerism access single product among numerous potential isomeric byproducts. Here,...
Because internal alkenes are more challenging synthetic targets than terminal alkenes, metal-catalyzed olefin mono-transposition (i.e., positional isomerization) approaches have emerged to afford valuable E- or Z- from their complementary alkene feedstocks. However, the applicability of these methods has been hampered by lack generality, commercial availability precatalysts, and scalability. Here, we report a nickel-catalyzed platform for stereodivergent E/Z-selective synthesis at room...
An asymmetric 1,2-dicarbofunctionalization of unactivated alkenes with aryl iodides and aryl/alkenylboronic esters under nickel/bioxazoline catalysis is disclosed. A wide array alkenyl nucleophiles are tolerated, furnishing the products in good yield high enantioselectivity. In addition to terminal alkenes, 1,2-disubstituted internal participate reaction, establishing two contiguous stereocenters diastereoselectivity moderate combination experimental computational techniques shed light on...
Abstract Because internal alkenes are more challenging synthetic targets than terminal alkenes, metal‐catalyzed olefin mono‐transposition (i.e., positional isomerization) approaches have emerged to afford valuable E ‐ or Z‐ from their complementary alkene feedstocks. However, the applicability of these methods has been hampered by lack generality, commercial availability precatalysts, and scalability. Here, we report a nickel‐catalyzed platform for stereodivergent / Z ‐selective synthesis at...
A stereodivergent, W-catalyzed alkene isomerization is reported, leading to either E - or Z -β,γ-unsaturated carbonyl compounds based on the ligand environment around metal.
Over the last fifty years, use of nickel catalysts for facilitating organic transformations has skyrocketed. Ni(0) sources act as useful precatalysts because they can enter a catalytic cycle through ligand exchange, without needing to undergo additional elementary steps. However, most are synthesized with stoichiometric aluminum–hydride reductants, pyrophoric reagents that not atom-economical and must be used at cryogenic temperatures. Here, we demonstrate Ni(II) salts reduced on preparative...
We report that the silylation of five-membered ring heteroarenes occurs with high sterically derived regioselectivity when catalyzed by combination of[Ir(cod)(OMe)]2 and a phenanthroline ligand or new pyridylimidazoline further increases regioselectivity. The reactions these catalysts produce yields heteroarylsilanes from functionalization at most accessible C–H bonds rings under conditions borylation previously reported formed mixtures products are unstable.