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Synthesis of Nixantphos Core-Functionalized Amphiphilic Nanoreactors and Application to Rhodium-Catalyzed Aqueous Biphasic 1-Octene Hydroformylation
Copyright policy )Synthesis of Nixantphos Core-Functionalized Amphiphilic Nanoreactors and Application to Rhodium-Catalyzed Aqueous Biphasic 1-Octene Hydroformylation
International audience; A latex of amphiphilic star polymer particles, functionalized in the hydrophobic core with nixantphos and containing P(MAA-co-PEOMA) linear chains in the hydrophilic shell (nixantphos-functionalized core-crosslinked micelles, or nixantphos@CCM), has been prepared in a one-pot three-step convergent synthesis using reversible addition-fragmentation chain transfer (RAFT) polymerization in water. The synthesis involves polymerization-induced self-assembly (PISA) in the second step and chain crosslinking with di(ethylene glycol) dimethacrylate (DEGDMA) in the final step. The core consists of a functionalized polystyrene, obtained by incorporation of a new nixantphos-functionalized styrene monomer (nixantphos-styrene), which is limited to 1 mol%. The nixantphos-styrene monomer was synthesized in one step by nucleophilic substitution of the chloride of 4-chloromethylstyrene by deprotonated nixantphos in DMF at 60 • C, without interference of either phosphine attack or self-induced styrene polymerization. The polymer particles, after loading with the [Rh(acac)(CO) 2 ] precatalyst to yield Rh-nixantphos@CCM, function as catalytic nanoreactors under aqueous biphasic conditions for the hydroformylation of 1-octene to yield n-nonanal selectively, with no significant amounts of the branched product 2-methyl-octanal.
Microsoft Academic Graph classification: Convergent synthesis Styrene chemistry.chemical_compound Polymer chemistry Reversible addition−fragmentation chain-transfer polymerization Chain transfer Monomer chemistry Polymerization Ethylene glycol Hydroformylation
Library of Congress Subject Headings: lcsh:QD241-441 lcsh:Organic chemistry
Polymers and Plastics, water-confined polymeric nanoreactors, Article, aqueous biphasic catalysis, hydroformylation, polymerization-induced self-assembly, RAFT polymerization, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, [CHIM.POLY]Chemical Sciences/Polymers, rhodium, nixantphos
Polymers and Plastics, water-confined polymeric nanoreactors, Article, aqueous biphasic catalysis, hydroformylation, polymerization-induced self-assembly, RAFT polymerization, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, [CHIM.POLY]Chemical Sciences/Polymers, rhodium, nixantphos
Microsoft Academic Graph classification: Convergent synthesis Styrene chemistry.chemical_compound Polymer chemistry Reversible addition−fragmentation chain-transfer polymerization Chain transfer Monomer chemistry Polymerization Ethylene glycol Hydroformylation
Library of Congress Subject Headings: lcsh:QD241-441 lcsh:Organic chemistry
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International audience; A latex of amphiphilic star polymer particles, functionalized in the hydrophobic core with nixantphos and containing P(MAA-co-PEOMA) linear chains in the hydrophilic shell (nixantphos-functionalized core-crosslinked micelles, or nixantphos@CCM), has been prepared in a one-pot three-step convergent synthesis using reversible addition-fragmentation chain transfer (RAFT) polymerization in water. The synthesis involves polymerization-induced self-assembly (PISA) in the second step and chain crosslinking with di(ethylene glycol) dimethacrylate (DEGDMA) in the final step. The core consists of a functionalized polystyrene, obtained by incorporation of a new nixantphos-functionalized styrene monomer (nixantphos-styrene), which is limited to 1 mol%. The nixantphos-styrene monomer was synthesized in one step by nucleophilic substitution of the chloride of 4-chloromethylstyrene by deprotonated nixantphos in DMF at 60 • C, without interference of either phosphine attack or self-induced styrene polymerization. The polymer particles, after loading with the [Rh(acac)(CO) 2 ] precatalyst to yield Rh-nixantphos@CCM, function as catalytic nanoreactors under aqueous biphasic conditions for the hydroformylation of 1-octene to yield n-nonanal selectively, with no significant amounts of the branched product 2-methyl-octanal.