Gold Phosphonates as Transfer Agents in Palladium Catalyzed Hirao Reactions

Through a cross-coupling reaction, aryl phosphonates are produced in high yields when the corresponding aryl bromides are reacted with a gold phosphorylating agent in the presence of a palladium catalyst and an appropriate ligand. To the best of our knowledge, this transformation is the first example involving the transfer of a phosphonate functional group from a gold complex to palladium that has been reported. Throughout the investigation, three gold phosphorylating agents were screened for activity towards the phosphorylation of aryl bromides. Aryl bromides with electrondonating and electron-withdrawing groups were successfully employed in the crosscoupling reactions. All cross-coupling reactions were carried out in THF at room temperature (25ºC) or in a microwave reactor (CEM Discover) at 60ºC for 30 or 60 minutes. The effects of changing reaction parameters such as time, temperature, catalyst and free ligand loading have been investigated. All aryl bromide substrates tested in the cross-coupling reactions produced phosphorylated products.

Dimerization of Poly(methyl methacrylate) Chains Using Radical Trap-Assisted Atom Transfer Radical Coupling

End-brominated poly(methyl methacrylate) (PMMABr) was prepared by atom transfer radical polymerization (ATRP) and employed in a series of atom transfer radical coupling (ATRC) and radical trap-assisted ATRC (RTA-ATRG) reactions. When coupling reactions were performed in the absence of a nitroso radical trap-traditional ATRC condition-very little coupling of the PMMA chains was observed, consistent with disproportionation as the major termination pathway for two PMMA chain-end radicals in our reactions. When 2-methyl-2-nitrosopropane (MNP) was used as the radical trap, coupling of the PMMA chains in this attempted RTA-ATRC reaction was again unsuccessful, owing to capping of the PMMA chains with a bulky nitroxide and preventing further coupling. Analogous reactions performed using nitrosobenzene (NBz) as the radical trap showed significant dimerization, as observed by gel permeation chromatography (GPC) by a shift in the apparent molecular weight compared to the PMMABr precursors. The extent of coupling was found to depend on the concentrion of NBz compared to the PMMABr chain ends, as well as the temperature and time of the coupling reaction. To a lesser extent, the concentrations of copper(I) bromide (CuBr), nitrogen ligand (N,N,N',N',N"-pentamethyldiethylenetriamine = PMDETA), and elemental copper (Cu) were also found to play a role in the success of the RTA-ATRC reaction. The highest levels of dimerization were observed when the coupling reaction was carried out at 80 degrees C for 0.5h, with ratio of 1:4:2.5:8:1 equiv of NBz: CuBr:Cu:PMDETA:PMMABr.

Selective Formation of Diblock Copolymers Using Radical Trap-Assisted Atom Transfer Radical Coupling

Polystyrene (PSt) radicals and poly(methyl acrylate) (PMA) radicals, derived from their monobrominated precursors prepared by atom transfer radical polymerization (ATRP), were formed in the presence of the radical trap 2-methyl-2-nitrosopropane (MNP), selectively forming PSt-PMA diblock copolymers with an alkoxyamine at the junction between the block segments. This radical trap-assisted, atom transfer radical coupling (RTA-ATRC) was performed in a single pot at low temperature (35 °C), while analogous traditional ATRC reactions at this temperature, which lacked the radical trap, resulted in no observed coupling and the PStBr and PMABr precursors were simply recovered. Selective formation of the diblock under RTA-ATRC conditions is consistent with the PStBr and PMABr having substantially different KATRP values, with PSt radicals initially being formed and trapped by the MNP and the PMA radicals being trapped by the in situ-formed nitroxide end-capped PSt. The midchain alkoxyamine functionality was confirmed by thermolysis of the diblock copolymer, resulting in recovery of the PSt segment and degradation of the PMA block at the relatively high temperatures (125 °C) required for thermal cleavage. A PSt-PMA diblock formed by chain extenstion ATRP using PStBr as the macroinitiator (thus lacking the alkoxyamine between the PSt-PMA segements) was inert to thermolysis. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3619–3626

Selective Formation of Diblock Copolymers Using Radical Trap-Assisted Atom Transfer Radical Coupling

Polystyrene (PSt) radicals and poly(methyl acrylate) (PMA) radicals, derived from their monobrominated precursors prepared by atom transfer radical polymerization (ATRP), were formed in the presence of the radical trap 2-methyl-2-nitrosopropane (MNP), selectively forming PSt-PMA diblock copolymers with an alkoxyamine at the junction between the block segments. This radical trap-assisted, atom transfer radical coupling (RTA-ATRC) was performed in a single pot at low temperature (35 degrees C), while analogous traditional ATRC reactions at this temperature, which lacked the radical trap, resulted in no observed coupling and the PStBr and PMABr precursors were simply recovered. Selective formation of the diblock under RTA-ATRC conditions is consistent with the PStBr and PMABr having substantially different K-ATRP values, with PSt radicals initially being formed and trapped by the MNP and the PMA radicals being trapped by the in situ-formed nitroxide end-capped PSt. The midchain alkoxyamine functionality was confirmed by thermolysis of the diblock copolymer, resulting in recovery of the PSt segment and degradation of the PMA block at the relatively high temperatures (125 degrees C) required for thermal cleavage. A PSt-PMA diblock formed by chain extenstion ATRP using PStBr as the macroinitiator (thus lacking the alkoxyamine between the PSt-PMA segements) was inert to thermolysis. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3619-3626

The Synthesis of Macrocyclic Polystyrene by Sequential Atom Transfer Radical Reactions

A method for the production of macrocyclic polystyrene via ring closing of a linear !,"-dibrominated polystyrene by an Atom Transfer Radical Coupling (ATRC) reaction is described. The dibrominated polystyrene chain was produced from two simultaneous atom transfer radical polymerizations (ATRPs) originating from a dibrominated benzal bromide initiator. To ensure the retention of the halogen end groups polymerization was allowed to proceed to less than 50% conversion. Using this precursor in an intramolecular ATRC (ring closing) reaction was found to yield in excess of 90% cyclic product based on refractive index-gel permeation chromatography (GPC) analysis. The cyclic architecture of the polymer was verified by GPC, Nuclear Magnetic Resonance (NMR), and mass spectrometry analysis. The utility of this method has been expanded by the addition of 2-methyl-2-nitrosopropane to the coupling reaction, which allows for the coupling to proceed at a faster rate and to yield macrocycles with incorporated alkoxyamine functionality. The alkoxyamine functionality allows for degradation of the cycles at high temperatures (>125° C) and we hypothesize that it may allow the macrocycles to act as a macroinitiator for a ring expansion polymerization in future studies.

Synthesis Of Triblock Copolymers By Radical Trap Assisted-Atom Transfer Radical Coupling

Monobrominated diblock copolymers composed of poly(styrene) (PSt), poly(methylacrylate) (PMA), or poly(methyl methacrylate) (PMMA) were synthesized by consecutive atom transfer radical polymerizations (ATRP). The brominated diblocks were utilized in atom transfer radical coupling (ATRC) and radical trap-assisted ATRC (RTA-ATRC) reactions to form ABA type triblock copolymers. Once PMMA-PStBr and PSt-PMABrBr were produced by ATRP, the synthes of PSt-PMA-PSt and PMMA-PSt- PMMA by ATRC and also by RTA-ATRC were attempted. The coupling methods were compared and it was found that RTA-ATRC succeeded in synthesizing PSt-PMA-PSt where ATRC could not, and that RTA-ATRC improved coupling over ATRC for PMMAPSt- PMMA. Incorporation of the radical trap 2-methyl-2-nitrosopropane (MNP) midchain allowed for simple thermal cleavage of the triblock to confirm the RTA-ATRC pathway occurred in preference over the head to head radical coupling pathway of ATRC. Triblocks made by ATRC did not cleave under our conditions, as no MNP was present and thus no labile C-O bond was incorporated. The RTA-ATRC pathway allowed for lower catalyst amounts (2 molar equivalents of copper(I)bromide and 2 molar equivalents of copper metal) and a high degree of coupling at lower temperatures (40°C). The RTA-ATRC improved upon ATRC because of its ability to generate a persistent radical and proceed by first order kinetics with respect to the chain end radical.