Designing Phase Selectively Soluble Polymer-Supports for Dimethylaminopyridine and Phosphine-Ligated Pd(0) Catalysts

Khamatnurova, Tatyana; Johnson, Mitchel; Santana, David Herrera; Bazzi, Hassan S.; Bergbreiter, David E.

doi:10.1007/s11244-014-0315-3

Cited by 7 publications

(11 citation statements)

References 14 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…RAFT‐based synthesis of single‐chain nanoparticles, core cross‐linked micelles, porous networks, and soluble polymers bearing phosphine functionalities as polymeric supports for transition metal catalyzed organic transformations has received recent attention within the scientific community. A common monomer used in this context has been the commercially available phosphine‐functional styrenic 4‐(diphenylphosphino)styrene (DPPS), with several reports focusing on its copolymerization with other styrenic monomers .…”

Section: Resultsmentioning

confidence: 99%

“…RAFT offers unparalleled functional group tolerance compared to other reversible deactivation radical polymerization techniques, allowing for control over the polymerization of a wide range of functional monomers, including less activated monomers (LAMs,) such as vinyl esters, vinylamides, N ‐vinyl heteroaromatics, and vinyl phosphonates which are typically difficult to control. Importantly RAFT is compatible with phosphine functionality as illustrated through the use of RAFT agents containing either free or complexed phosphines and the polymerization of phosphine‐containing monomers . Furthermore, RAFT is relatively simple to implement, with reaction conditions often differing from a conventional radical polymerization only by the addition of a RAFT agent.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Phosphorus‐Containing Gradient (Block) Copolymers via RAFT Polymerization and Postpolymerization Modification

Sykes

Harrisson

Keddie

2016

Macro Chemistry & Physics

View full text Add to dashboard Cite

Reversible addition-fragmentation chain transfer (RAFT) copolymerization of styrene (St) and 4-(diphenylphosphino)styrene (DPPS) is explored to establish the statistical distribution of the phosphine-functional monomer within the copolymer. RAFT copolymerization of St and DPPS at a variety of feed ratios provides phosphine-functional copolymers of low dispersity at moderate monomer conversion (Ð <1.2 at conv. >60%). In all cases the fraction of DPPS in the resulting polymers is greater than that in the monomer feed. Estimation of copolymerization reactivity ratios indicates DPPS has a strong tendency to homopolymerize whilst St preferentially copolymerizes with DPPS (r DPPS = 4.4; r St = 0.31). The utility of the copolymers as macro-RAFT agents in block copolymer synthesis is demonstrated via chain extension with hydrophilic acrylamide (N,N-dimethylacrylamide (DMAm)) and acrylate a Supporting Information is available online from the Wiley Online Library or from the corresponding author.-2 -(poly(ethylene glycol) methyl ether acrylate (mPEGA); di(ethylene glycol) ethyl ether acrylate (EDEGA)) monomers. Finally access to polymers containing phosphine oxide and phosphonium salt functionalities is shown through post-polymerization modification of the phosphine-containing copolymers.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Phosphorus‐Containing Gradient (Block) Copolymers via RAFT Polymerization and Postpolymerization Modification

Sykes

Harrisson

Keddie

2016

Macro Chemistry & Physics

View full text Add to dashboard Cite

show abstract

“…This is an approach with considerable precedent at least for conventional phosphine ligands. 19,20 Results and discussion 16 Alternative strategies have also been used.…”

Section: Introductionmentioning

confidence: 99%

“…[19][20][21] The first 4-alkyl-substituted polystyrene support is an alternative to unsubstituted polystyrene. [19][20][21] The first 4-alkyl-substituted polystyrene support is an alternative to unsubstituted polystyrene.…”

Section: Introductionmentioning

confidence: 99%

“…Thus, we chose to use copolymers with a ca. 20 The terpolymer 4 was characterized by GPC and 1 H NMR spectroscopy and contained 7 mol% -CH 2 Cl groups based on 1 H NMR spectroscopy analysis of the relative peaks at 2.47 δ for the benzylic protons of the 4-dodecylstyrene groups and at 4.45 δ for the -CH 2 Cl protons of the chloromethyl group. Such polyĲ4-alkylstyrene)s have previously been shown to afford highly phase selective supports for organocatalysts.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Soluble polymer-supported hindered phosphine ligands for palladium-catalyzed aryl amination

Khamatnurova

Zhang

Suriboot

et al. 2015

Catal. Sci. Technol.

Self Cite

View full text Add to dashboard Cite

Strategies for synthesis of more effective soluble supported ligands for phosphine-ligated Pd(0) cross coupling catalysts have been explored. Reversible addition-fragmentation chain transfer (RAFT) polymerization has been used to prepare alkane-soluble polyĲ4-alkylstyrene)-bound phosphine ligands. 4-tert-Butylstyrene and 4-dodecylstyrene were copolymerized with ca. 7 mol% of 4-chloromethylstyrene or a 4-diphenylphosphinestyrene monomer using RAFT chemistry to afford polyĲtert-butylstyrene-co-4dodecylstyrene) copolymers. Polymers with chloromethyl groups were allowed to react with the phenolic group of a hindered dicyclohexylbiarylphosphine ligand. This hindered polymer-bound phosphine formed reactive Pd complexes useful in haloarene amine couplings. All aryl halide amination reactions had Pd leaching that was typically <0.1% of the charged Pd with one example having only 0.02% Pd leaching. These Pd complexes of polyĲ4-alkylstyrene)-bound phosphines were also compared to similar hindered phosphine complexes formed with a polyisobutylene (PIB), whose terminus was also converted into a dicyclohexylbiarylphosphine ligand. Palladium catalysts ligated by these hindered biarylphosphines on polyĲ4-alkylstyrene) and PIB-bound both were recyclable in the absence of oxygen, had similar activity, and very low Pd leaching.

show abstract

Versatile soluble oligomeric styrene supports for peptide synthesis

Erapalapati

Madhavan

2015

J. Polym. Sci. Part A: Polym. Chem.

View full text Add to dashboard Cite

Soluble oligomeric styrene supports are reported here with high loading capacities of 1.5–1.6 mmol/g similar to resins used in solid phase peptide synthesis. Oligoether and alkyl chains are incorporated into the scaffold to improve the support solubility and act as spacers between the attachment sites. Amino acids have been attached to the support in 59–85% yields and 0.87–1.3 mmol/g loading. The supports have been used to synthesize tri‐ to hexapeptides in 38–64% yields using only 2 equivalents of coupling reagents, which is much lower than the amount of reagents typically used in solid phase synthesis. A modular synthetic approach is used to obtain the supports so that any efficient styrene‐based attachment site can be readily incorporated into our soluble support scaffold. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 2501–2509

show abstract

Designing Phase Selectively Soluble Polymer-Supports for Dimethylaminopyridine and Phosphine-Ligated Pd(0) Catalysts

Cited by 7 publications

References 14 publications

Phosphorus‐Containing Gradient (Block) Copolymers via RAFT Polymerization and Postpolymerization Modification

Phosphorus‐Containing Gradient (Block) Copolymers via RAFT Polymerization and Postpolymerization Modification

Soluble polymer-supported hindered phosphine ligands for palladium-catalyzed aryl amination

Versatile soluble oligomeric styrene supports for peptide synthesis

Contact Info

Product

Resources

About