2015
DOI: 10.1039/c5dt02364e
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Phosphane–ene chemistry: the reactivity of air-stable primary phosphines and their compatibility with the thiol–ene reaction

Abstract: Air-sensitive and air-stable primary phosphines (RPH2) were compared for their ability to undergo photoinitiated phosphane-ene chemistry with 1-hexene. Despite their increased air-stability, the primary phosphines displayed equal to or greater reactivity when compared to air-sensitive alkyl or aryl analogues. The phosphane-ene reaction was also performed in the presence of 1-octanethiol to determine whether thiol-ene and phosphane-ene chemistries could proceed simultaneously. It was determined that the phospha… Show more

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Cited by 11 publications
(11 citation statements)
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References 34 publications
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“…During the formation of 1 a – f and 2 a – f , reactions with the aliphatic phosphines showed qualitatively faster rates than those with the aromatic phosphine (Table 1). These relative rates mimic those observed in the hydrophosphination of olefins [27] . A corresponding electronic trend for the imine was observed for Entries d‐f.…”
Section: Resultssupporting
confidence: 75%
See 1 more Smart Citation
“…During the formation of 1 a – f and 2 a – f , reactions with the aliphatic phosphines showed qualitatively faster rates than those with the aromatic phosphine (Table 1). These relative rates mimic those observed in the hydrophosphination of olefins [27] . A corresponding electronic trend for the imine was observed for Entries d‐f.…”
Section: Resultssupporting
confidence: 75%
“…A lower conversion efficiency was achieved with PhPH 2 ( � 40 %), which is consistent with its sluggish addition to C=C bonds and underscores that more electron rich phosphines drive the equilibrium toward hydrophosphination products. [27] The ratio of 1 c : 2 c is 3 : 1, and this reflects the intermediate steric profile of Ph as compared to i-Bu and Cy.…”
Section: Resultsmentioning
confidence: 98%
“…In contrast, conventional radical-mediated vinyl chain growth polymerizations and indeed the iodo–ene polymerization do not embody click chemistry as they exclusively generate carbon–carbon bonds. Nevertheless, as demonstrated here and by others, ,, the APT polymerization mechanism is not exclusive to thiol-based chain transfer agents, and thus this unique mechanism is a framework for expanding the toolkit of spatially and temporally controllable, radical-mediated, step-growth polymerization chemistries with potential for new cross-linked materials.…”
mentioning
confidence: 60%
“…This polymerization mechanism was found to be insensitive to oxygen, a trait shared with thiol–ene reactions, yet its efficiency was low, attributable to the relatively high bond dissociation energy of the Si–H moiety. Building upon the addition of phenylphosphine to divinyl monomers to generate linear polymers, radical-mediated phosphane–ene photopolymerizations were recently described where air-stable, primary phosphines were added to multifunctional allylic monomers. , Notably, as the primary phosphines exhibited bireactivity as APT donors, the synthesis of a cross-linked polymer was demonstrated using a monophosphine/triallyl monomer formulation . Halide-based chain transfer agents demonstrate an enhanced capacity for chain transfer via atom abstraction .…”
mentioning
confidence: 99%
“…13 They are remarkably stable towards air and moisture, redox active, and afford the ability to tune their steric properties through the sequential addition of ethylmetallocene units. Herein, we present a comprehensive study of the structure, bonding, and properties of a series of Group 6 metal pentacarbonyl (M = Cr, Mo, W) complexes of primary, secondary, and tertiary ferrocenylethylphosphines in order to establish fundamental knowledge of their ligand characteristics.…”
mentioning
confidence: 99%