Phosphines and related C–P bonded compounds

Allen, David W.

doi:10.1039/9781782626930-00001

Cited by 13 publications

(5 citation statements)

References 375 publications

(485 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[1] Classic synthetic methodologies for phosphine preparation have major drawbacks,i ncluding poor functional-group tolerance,s ide-product formation, the use of protecting groups and stoichiometric amounts of additives,w hich is as ignificant disadvantage for atom economy. [1] Classic synthetic methodologies for phosphine preparation have major drawbacks,i ncluding poor functional-group tolerance,s ide-product formation, the use of protecting groups and stoichiometric amounts of additives,w hich is as ignificant disadvantage for atom economy.…”

Section: Organophosphoruscompoundsareavitalclassofchemicalsmentioning

confidence: 99%

Iron(II)‐Catalyzed Hydrophosphination of Isocyanates

et al. 2017

View full text Add to dashboard Cite

The first transition metal catalyzed hydrophosphination of isocyanates is presented. The use of low-coordinate iron(II) precatalysts leads to an unprecedented catalytic double insertion of isocyanates into the P-H bond of diphenylphosphine to yield phosphinodicarboxamides [Ph PC(=O)N(R)C(=O)N(H)R], a new family of derivatized organophosphorus compounds. This remarkable result can be attributed to the low-coordinate nature of the iron(II) centers whose inherent electron deficiency enables a Lewis-acid mechanism in which a combination of the steric pocket of the metal center and substrate size determines the reaction products and regioselectivity.

show abstract

Section: Organophosphoruscompoundsareavitalclassofchemicalsmentioning

confidence: 99%

Iron(II)‐Catalyzed Hydrophosphination of Isocyanates

et al. 2017

View full text Add to dashboard Cite

show abstract

“…Organophosphines are integral molecules in catalysis, synthetic chemistry, materials science, and more. − Metal-catalyzed hydrophosphination, the addition of a P–H bond across an unsaturated substrate, is one of the most promising and atom-economical P–C bond-forming reactions. − Progress has been made in expanding the available catalysts, scope, and selectivity of hydrophosphination in recent years. − However, limitations remain that hamper the synthetic utility of hydrophosphination. , Among the most notable limitations with known catalysts is that they often require special preparation and/or complex ancillary ligands and that most precatalysts are not air- and water-stable (i.e., not convenient). Known catalysts also have limitations in reactivity, often stymied by unactivated or highly substituted substrates, especially in intermolecular reactions. , …”

Section: Introductionmentioning

confidence: 99%

Divergent Mechanistic Pathways for Copper(I) Hydrophosphination Catalysis: Understanding That Allows for Diastereoselective Hydrophosphination of a Tri-substituted Styrene

et al. 2022

View full text Add to dashboard Cite

Readily available and bench-stable Cu(acac) 2 (1) addresses many challenges in exploratory hydrophosphination catalysis. Mechanistic investigations were performed to answer questions that remain about the reactivity of 1, the role of light in catalysis, and to provide direction for further study. A divergent Hammett plot indicates different mechanisms based on electron density at the alkene substrate. A radical process was eliminated based on trapping reactions and in situ electron paramagnetic resonance experiments. Isotopic labeling experiments, a zwitterionic trapping experiment, stoichiometric model reactions, and catalytic reactions using proxy intermediates indicate that both the conjugate addition and insertion-based mechanistic pathways occur with this system, depending on the unsaturated substrate. Computational analysis indicates that the lowest energy transition is a ligand-to-metal charge transfer from the phosphido ligand where the LUMO has significant Cu−P antibonding character, suggesting that a weakened Cu−P bond accelerates insertion under photocatalytic conditions. This hypothesis explains the greater activity of 1 compared to prior copper-catalyzed hydrophosphination reports and appears to be a general phenomenon for copper(I) catalysts. These results have been leveraged to achieve heretofore unknown catalytic hydrophosphination reactivity, namely the diastereoselective hydrophosphination of a tri-substituted styrene substrate.

show abstract

“…with extensive commercial applications. [1] Classic synthetic methodologies for phosphine preparation have major drawbacks,i ncluding poor functional-group tolerance,s ide-product formation, the use of protecting groups and stoichiometric amounts of additives,w hich is as ignificant disadvantage for atom economy. [2] Therefore,t here is growing demand to develop atom-economical routes for the preparation of functionalized phosphines.Inparticular, hydrophosphination is an attractive synthetic route to phosphine products, proceeding by PÀHb ond addition across aC -C/X (X = O, N, S) multiple bond.…”

Section: Organophosphoruscompoundsareavitalclassofchemicalsmentioning

confidence: 99%

Iron(II)‐Catalyzed Hydrophosphination of Isocyanates

et al. 2017

View full text Add to dashboard Cite

The first transition metal catalyzedh ydrophosphination of isocyanates is presented. The use of low-coordinate iron(II) precatalysts leads to an unprecedented catalytic double insertion of isocyanates into the P À Hb ond of diphenylphosphine to yield phosphinodicarboxamides [Ph 2 PC(=O)N(R)-C(=O)N(H)R],anew family of derivatized organophosphorus compounds.This remarkable result can be attributed to the low-coordinate nature of the iron(II) centers whose inherent electron deficiency enables aL ewis-acid mechanism in which ac ombination of the steric pocket of the metal center and substrate sizedetermines the reaction products and regioselectivity.Supportinginformation (full experimental details for the hydrophosphination reactions, reaction monitoring by NMR spectroscopy, crystallographic data) and the ORCID identification number(s) for the author(s) of this article can be found under:http://dx.

show abstract

Phosphines and related C–P bonded compounds

Cited by 13 publications

References 375 publications

Iron(II)‐Catalyzed Hydrophosphination of Isocyanates

Iron(II)‐Catalyzed Hydrophosphination of Isocyanates

Divergent Mechanistic Pathways for Copper(I) Hydrophosphination Catalysis: Understanding That Allows for Diastereoselective Hydrophosphination of a Tri-substituted Styrene

Iron(II)‐Catalyzed Hydrophosphination of Isocyanates

Contact Info

Product

Resources

About