A Catalytic Collaboration: Pairing Transition Metals and Lewis Acids for Applications in Organic Synthesis DOI

A. Dina Dilinaer,

Gabriel J. Jobin,

Marcus W. Drover

et al.

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(32), P. 13298 - 13307

Published: Jan. 1, 2024

The use of metal catalysts to accelerate an organic transformation has proven indispensable for access structural motifs having applications across medicinal, polymer, materials chemistry, and more. Most catalytic approaches have cast transition metals in the "leading role"; these players mediate important reactions such as C-C cross coupling hydrogenation unsaturated bonds. These may require collaboration, featuring Lewis acidic or basic additives promote a desired reaction outcome. acids can serve by way substrate stabilization and/or activation, such, are valuable optimizing transformations. A burgeoning area chemical research which unifies concepts thus sought develop complexes ambiphilic (containing unit) ligands. This approach takes advantage metal-ligand cooperativity increase efficiency given transformation, leveraging intramolecular interactions between adjacent secondary ligand site. While this shown significant potential facilitate challenging transformations, there remains unexplored depth creativity future advancement.

Language: Английский

Secondary-sphere preorganization enables nickel-catalyzed nitrile hydroboration DOI
Medina Afandiyeva, Xijue Wu, William W. Brennessel

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(90), P. 13450 - 13453

Published: Jan. 1, 2023

Herein, we describe nickel-catalyzed nitrile hydroboration with pinacolborane, wherein a tethered NHC-pyridonate ligand enables efficient catalysis (5 mol% [Ni], ≤6 h reaction time) at room temperature. Mechanistic studies, including isolation of the catalytically relevant intermediates, shed light on cooperative role in activating both reagents simultaneously.

Language: Английский

Citations

10
Ynone Co-Coordination at a Nickel Borane Complex: An Assessment of Secondary Coordination Sphere Effects DOI
Marissa L. Clapson,

A. Dina Dilinaer,

Trisha C. Q. Lanaque

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(14), P. 6184 - 6191

Published: March 28, 2024

Secondary coordination sphere ligand effects can be used to direct or organize small molecule substrates at a metal center. Herein, we assess the bifunctional ambiphilic diphosphine, tri-tert-butylboranyldiphosphinoethane (ttbbpe) and its ability influence stereoselective substrate coordination, while appended nickel. This report takes synthetic/computational approach test impacts limitations associated with ligand-directed using [Ni(ttbbpe)(η2:η2-COD)] (COD = 1,5-cyclooctadiene) ynones (alkynes having an α-carbonyl group propargylic position) as model substrates.

Language: Английский

Citations

1
Anomalous Hydroboration at a Four-Coordinate Ni(II) Diphenylvinylphosphine Complex: Geometric Impacts on Solution Equilibria DOI
Marissa L. Clapson, Brady J. H. Austen, Joseph A. Zurakowski

et al.

Organometallics, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 3, 2024

For coordination compounds, reliable control of metal geometry and spin state is great interest, permitting reactivity selectivity. As tuneable outputs, these observables are adjusted through thoughtful choice ligand. This report examines a family monophosphine-ligated nickel(II) dihalide compounds containing secondary sphere borane groups. Interestingly, anomalous hydroboration trans-[NiII(X)2(PPh2Vin)2] (Vin = vinyl) was witnessed upon treatment with HBCy2 (Cy cyclohexyl), resulting in halide-directed Markovnikov hydroboration; branched products were observed to be diamagnetic solution. outcome contrast the linear ligand variants, which prepared independently show solution paramagnetism. Together, this details an unusual how gives way unique behavior simply by virtue or incorporation.

Language: Английский

Citations

0
Tridentate κ3-P,P,C Iridium Complexes: Influence of Ligand Saturation on Intramolecular C—H Bond Activation DOI
Mitchell J. Demchuk, Joseph A. Zurakowski, Marcus W. Drover

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(59), P. 7566 - 7569

Published: Jan. 1, 2024

Whereas κ 3 - P , C -based donor ligands are ubiquitous across synthetic chemistry, related unsymmetric systems having -coordination comparatively rare.

Language: Английский

Citations

0
A Catalytic Collaboration: Pairing Transition Metals and Lewis Acids for Applications in Organic Synthesis DOI

A. Dina Dilinaer,

Gabriel J. Jobin,

Marcus W. Drover

et al.

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(32), P. 13298 - 13307

Published: Jan. 1, 2024

The use of metal catalysts to accelerate an organic transformation has proven indispensable for access structural motifs having applications across medicinal, polymer, materials chemistry, and more. Most catalytic approaches have cast transition metals in the "leading role"; these players mediate important reactions such as C-C cross coupling hydrogenation unsaturated bonds. These may require collaboration, featuring Lewis acidic or basic additives promote a desired reaction outcome. acids can serve by way substrate stabilization and/or activation, such, are valuable optimizing transformations. A burgeoning area chemical research which unifies concepts thus sought develop complexes ambiphilic (containing unit) ligands. This approach takes advantage metal-ligand cooperativity increase efficiency given transformation, leveraging intramolecular interactions between adjacent secondary ligand site. While this shown significant potential facilitate challenging transformations, there remains unexplored depth creativity future advancement.

Language: Английский

Citations

0