Aryl pyrrolidinones via radical 1,4-aryl migration and 5-endo-trig cyclisation of N-(2-bromoallyl)arylcarboxamides

Radical reaction of a series of N-(2-bromoallyl)arylcarboxamides led to the production of 4-arylpyrrolidin-2-ones and directly reduced materials in comparable yields. A cascade process, involving sequential 5-exo-trig spirocyclisation, β-scission, and 5-endo-trig cyclisation of the resulting acyl radical, is proposed to explain the pyrrolidinone products.     

Catalyst‐Driven Scaffold Diversity: Selective Synthesis of Spirocycles,Carbazoles and Quinolines from Indolyl Ynones

Medicinally relevant spirocyclic indolenines, carbazoles and quinolines can each be directly synthesised selectively from common indolyl ynone starting materials by catalyst variation. The high yielding, divergent reactions all proceed by an initial dearomatising spirocyclisation reaction to generate an intermediate vinyl–metal species, which then rearranges selectively by careful choice of catalyst and reaction conditions.     

Substrate‐Tuned Catalysis of the Radical S‐Adenosyl‐L‐Methionine Enzyme NosL Involved in Nosiheptide Biosynthesis

NosL is a radical S‐adenosyl‐L ‐methionine (SAM) enzyme that converts L ‐Trp to 3‐methyl‐2‐indolic acid, a key intermediate in the biosynthesis of a thiopeptide antibiotic nosiheptide. In this work we investigated NosL catalysis by using a series of Trp analogues as the molecular probes. Using a benzofuran substrate 2‐amino‐3‐(benzofuran‐3‐yl)propanoic acid (ABPA), we clearly demonstrated that the 5′‐deoxyadenosyl (dAdo) radical‐mediated hydrogen abstraction in NosL catalysis is not from the indole nitrogen but likely from the amino group of L ‐Trp. Unexpectedly, the major product of ABPA is a decarboxylated compound, indicating that NosL was transformed to a novel decarboxylase by an unnatural substrate. Furthermore, we showed that, for the first time to our knowledge, the dAdo radical‐mediated hydrogen abstraction can occur from an alcohol hydroxy group. Our study demonstrates the intriguing promiscuity of NosL catalysis and highlights the potential of engineering radical SAM enzymes for novel activities.     

Biobased Polymers via Radical Homopolymerization and Copolymerization of a Series of Terpenoid-Derived Conjugated Dienes with exo-Methylene and 6-Membered Ring

A series of exo-methylene 6-membered ring conjugated dienes, which are directly or indirectly obtained from terpenoids, such as β-phellandrene, carvone, piperitone, and verbenone, were radically polymerized. Although their radical homopolymerizations were very slow, radical copolymerizations proceeded well with various common vinyl monomers, such as methyl acrylate (MA), acrylonitrile (AN), methyl methacrylate (MMA), and styrene (St), resulting in copolymers with comparable incorporation ratios of bio-based cyclic conjugated monomer units ranging from 40 to 60 mol% at a 1:1 feed ratio. The monomer reactivity ratios when using AN as a comonomer were close to 0, whereas those with St were approximately 0.5 to 1, indicating that these diene monomers can be considered electron-rich monomers. Reversible addition fragmentation chain-transfer (RAFT) copolymerizations with MA, AN, MMA, and St were all successful when using S-cumyl-S’-butyl trithiocarbonate (CBTC) as the RAFT agent resulting in copolymers with controlled molecular weights. The copolymers obtained with AN, MMA, or St showed glass transition temperatures (T_g) similar to those of common vinyl polymers (T_g ~ 100 °C), indicating that biobased cyclic structures were successfully incorporated into commodity polymers without losing good thermal properties.     

Copolymerization of vinyl acetate with 1-octene and ethylene by cobalt-mediated radical polymerization

The cobalt-mediated radical polymerization of vinyl acetate was extended to copolymerization with 1-alkenes (ethylene or 1-octene). In agreement with the low amount of 1-alkene that could be incorporated into the copolymer, a gradient structure was predictable, but a rather low polydispersity was observed. A poly(vinyl acetate)-b-poly(octene) copolymer was also successfully synthesized, leading to a poly (vinyl alcohol)-b-poly(octene) amphiphilic copolymer upon the methanolysis of the poly (vinyl acetate) block. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2532–2542, 2007     

Fragmentation of carbohydrate anomeric alkoxyl radicals. Synthesis of highly functionalized chiral vinyl sulfones

The reaction of derivatives of 3-acetyl-d-glucal, 3-acetyl-l-rhamnal, 3-acetyl-d-galactal, and 3-acetyl-d-lactal with sodium benzenesulfinate in acid medium catalyzed by HgSO₄ afforded diastereoisomeric mixtures of the corresponding 2,3-dideoxy-3-(phenylsulfonyl)-hexopyranoses through a Ferrier rearrangement. The anomeric alkoxyl radical fragmentation of these γ-hydroxy sulfones using the system (diacetoxyiodo)benzene and iodine gave vinyl sulfones with structures of 1,2-dideoxy-4-O-formyl-2-(phenylsulfonyl)-pent-1-enitol and configurations d-erythro, l-erythro, and d-threo at the two stereogenic centers.     

Key Role of Intramolecular Metal Chelation and Hydrogen Bonding in the Cobalt‐Mediated Radical Polymerization of N‐Vinyl Amides

This work reveals the preponderance of an intramolecular metal chelation phenomenon in a controlled radical polymerization system involving the reversible trapping of the radical chains by a cobalt complex bis(acetylacetonato)cobalt(II). The cobalt‐mediated radical polymerization (CMRP) of a series of N‐vinyl amides was considered with the aim of studying the effect of the cobalt chelation by the amide moiety of the last monomer unit of the chain. The latter reinforces the cobalt? polymer bond in the order N‐vinylpyrrolidone<N‐vinyl caprolactam<N‐methyl‐N‐vinyl acetamide, and is responsible for the optimal control of the polymerizations observed for the last two monomers. Such a double linkage between the controlling agent and the polymer, through a covalent bond and a dative bond, is unique in the field of controlled radical polymerization and represents a powerful opportunity to fine tune the equilibrium between latent and free radicals. Possible hydrogen bond formation is also taken into account in the case of N‐vinyl acetamide and N‐vinyl formamide. These results are essential for understanding the factors influencing Co? C bond strength in general, and the CMRP mechanism in particular, but also for developing a powerful platform for the synthesis of new precision poly(N‐vinyl amide) materials, which are an important class of polymers that sustain numerous applications today.     

Stereoselective synthesis of tri- and tetrasubstituted oxepanes via n-Bu3SnH mediated 7-endo-trig vinyl radical cyclisation

A stereoselective 7-endo-trig cyclisation of homopropargyl and phenyl homopropargyl derivatives of Baylis-Hillman adducts using n-Bu₃SnH/AIBN mediated vinyl radical cyclisation affords tri- and tetrasubstituted oxepanes, respectively, in good yields.     

Thermal and mechanical characterization of poly(vinyl chloride)-b-poly(butyl acrylate)-b-poly(vinyl chloride) obtained by single electron transfer - degenerative chain transfer living radical polymerization in water

This work reports the synthesis of several copolymers of poly(vinyl chloride)-b-poly(n-butyl acrylate)-b-Poly(vinyl chloride) prepared by single electron transfer/degenerative chain transfer mediated living radical polymerization (SET-DTLRP) in a two step process: first, a bifunctional macroinitiator of α,ω-di(iodo)poly(butyl acrylate) [α,ω-di(iodo)PBA] was synthesized by SET-DTLRP in water at 30 °C. The obtained macroinitiator was further reinitiated also by SET-DTLRP leading to the formation of the desired product. Several copolymers were synthesized in a 5L pilot reactor with different molecular weights and relative amounts of PBA and PVC. The possibility of synthesizing flexible materials made of PVC without using normal free plasticizes is extremely important for the industry. After processing the materials in a two-roll mill laboratorial equipment, the block copolymers were characterized concerning thermal and mechanical. The materials characterized in this study were prepared in a 5L pilot reactor under similar conditions to be used in industrial scale.     

Radical oxyamination of vinyl azides with N-hydroxyphthalimide under the action of [bis(trifluoroacetoxy)iodo]benzene

O,O′-Bis(phthalimido)-modified 2-(hydroxyimino)ethanols containing N–O–N fragment were synthesized in high yields via the reaction of vinyl azides with N-hydroxyphthalimide under the action of hypervalent iodine-based oxidant. The reaction proceeds under mild conditions and is compatible with a wide range of vinyl azides. Presumably, the process starts with the oxidative formation of phthalimide-N-oxyl radical, followed by its addition to vinyl azide with the subsequent trapping of the generated iminyl radical with the second phthalimide-N-oxyl radical.     

Controlled random and alternating copolymerization of (meth)acrylates,acrylonitrile, and (meth)acrylamides with vinyl ethers by organotellurium‐, organostibine‐, and organobismuthine‐mediated living radical polymerization reactions

Random and alternating copolymerizations of acrylates, methacrylates, acrylonitorile, and acrylamides with vinyl ethers under organotellurium‐, organostibine‐, and organobismuthine‐mediated living radical polymerization (TERP, SBRP, and BIRP, respectively) have been studied. Structurally well‐controlled random and alternating copolymers with controlled molecular weights and polydispersities were synthesized. The highly alternating copolymerization occurred in a combination of acrylates and vinyl ethers and acrylonitorile and vinyl ethers by using excess amount of vinyl ethers over acrylates and acrylonitorile. On the contrary, alternating copolymerization did not occur in a combination of acrylamides and vinyl ethers even excess amount of vinyl ethers were used. The reactivity of polymer‐end radicals to a vinyl ether was estimated by the theoretical calculations, and it was suggested that the energy level of singly occupied molecular orbital (SOMO) of polymer‐end radical species determined the reactivity. By combining living random and alternating copolymerization with living radical or living cationic polymerization, new block copolymers, such as (PBA‐alt‐PIBVE)‐block‐(PtBA‐co‐PIBVE), PBA‐block‐(PBA‐alt‐PIBVE), and (PTFEA‐alt‐PIBVE)‐block‐PIBVE, with controlled macromolecular structures were successfully synthesized. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

6-endo Versus 5-exo radical cyclization: streamlined syntheses of carbahexopyranoses and derivatives by 6-endo-trig radical cyclization

Three factors that can direct 6-endo radical cyclization over 5-exo ring closure: substitution at C-5, vinyl radical cyclization and ring strain, have been considered in the context of the preparation of carbapyranoses from carbohydrate derivatives. As a result, alkyl radicals in substrates containing a strain inducing 2,3-O-isopropylidene ring, and vinyl radical in non-strained compounds undergo a completely regioselective 6-endo-trig ring closure leading to carbasugar derivatives.     

Free radical polymerization of glycidyl methacrylate in plasticized Poly(vinyl chloride)

Kinetic of free radical in-situ polymerization of glycidyl methacrylate (GMA), was studied in a complex evolutionary system: poly(vinyl chloride) (PVC) plastisols. A predictive model of conversion-time profile based on free radical mechanism was proposed and structure of the modified PVC system developed was investigated by NMR analyses. In order to elucidate the mechanism of the reaction, model molecules for PVC were used with NMR and MALDI-TOF characterization. It was found that in-situ polymerization of GMA in PVC plastisols leads to both homopolymerization and grafting of GMA onto PVC backbone by hydrogen abstraction. For 33 wt% GMA loaded, grafting efficiency is 67% with an amount of grafted poly-glycidyl methacrylate (pGMA) equals to 22 wt%. Thus, this article discloses a new type of PVC plastisols called reactive plastisols where, in addition to usual plasticizers, PVC is modified by polymerizable GMA monomer.     

Synthesis of poly(tert‐butyl acrylate‐block‐vinyl acetate) copolymers by combining ATRP and RAFT polymerizations

The synthesis of poly(tert‐butyl acrylate‐block‐vinyl acetate) copolymers using a combination of two living radical polymerization techniques, atom transfer radical polymerization (ATRP) and reversible addition‐fragmentation chain transfer (RAFT) polymerization, is reported. The use of two methods is due to the disparity in reactivity of the two monomers, viz. vinyl acetate is difficult to polymerize via ATRP, and a suitable RAFT agent that can control the polymerization of vinyl acetate is typically unable to control the polymerization of tert‐butyl acrylate. Thus, ATRP was performed to make poly(tert‐butyl acrylate) containing a bromine end group. This end group was subsequently substituted with a xanthate moiety. Various spectroscopic methods were used to confirm the substitution. The poly(tert‐butyl acrylate) macro‐RAFT agent was then used to produce (tert‐butyl acrylate‐block‐vinyl acetate). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7200–7206, 2008     

Stereocontrol in radical polymerization

The stereospecific radical polymerization of vinyl esters, methacrylates, and alpha-substituted acrylates was studied. Fluoroalcohols, as a solvent, have remarkable effects on the stereoregularity of the radical polymerizations of vinyl acetate, vinyl pivalate, and vinyl benzoate, affording polymers rich in syndiotacticity, heterotacticity, and isotacticity, respectively. This method was successfully applied to the polymerization of methacrylates to give syndiotactic polymers. The steric repulsion between the entering monomer and the chain-end monomeric unit bound by the solvent through hydrogen bonding is important for the stereochemical control in these systems. Lewis acid catalysts, such as lanthanide trifluoromethanesulfonates and zinc salts, were also effective for the stereocontrol during the radical polymerization of methyl methacrylate, to reduce the syndiotacticity and alpha-(alkoxymethyl)acrylates to synthesize isotactic and syndiotactic polymers. Radical polymerization of the methacrylates bearing a bulky ester group, such as the triphenylmethyl methacrylate derivatives, gave highly isotactic polymers, as in the case of anionic polymerization. In addition, the control of one-handed helical conformation was attained in the radical polymerization of 1-phenyldibenzosuberyl methacrylate using chiral neomenthanethiol or cobalt(II) complexes as an additive.     

Free radical polymerization with catalytic chain transfer: Using NMR to probe the strength of the cobalt–carbon bond in small molecule model reactions

This work examines cobalt–carbon bond formation between the cobalt (II) macrocycle, (tetrakis(p‐methoxyphenyl)porphyrinato)cobalt (II), (TAP)Co, and a variety of radicals derived from vinyl compounds to facilitate a better understanding of the various factors affecting the cobalt–carbon bond strength in catalytic chain transfer polymerization. The reaction of (TAP)Co with the following vinylic molecules was studied: methacrylonitrile, cyclohexene, methyl methacrylate, styrene, methyl acrylate, vinyl acetate, vinyl benzoate, methyl crotonate, cis‐2‐pentenenitrile, and ethyl α‐hydroxymethacrylate. Different concentrations of each vinylic compound were added to (TAP)Co and 2,2′‐azobis(isobutyronitrile) in CDCl₃ at 60 °C. The ratio of Co(III) to Co(II) and the nature of the radical bound to the cobalt macrocycle were determined via nuclear magnetic resonance measurements. Several factors are shown to affect the reaction of the radical and the cobalt (II) species (and hence the strength of the cobalt–carbon bond in the resulting compound). These factors are as follows: the number of pathways by which a radical may be derived from the vinyl compound; the variety of radicals that can be produced from the vinylic molecule; the stability of the radical(s) generated; and the relative propagation rate of the vinyl compound. A discussion on the relevance of this study to the behavior of different monomers in catalytic chain transfer reactions is included. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6171–6189, 2006     

Synthesis and biodegradation studies of new copolymers based on sucrose derivatives and styrene

Novel unsaturated esters of sucrose were synthesised directly and in good yields from sucrose using a simple, mild, and selective Mitsunobu procedure. These regioisomerically pure vinyl sugars have been copolymerised with styrene by a free radical process, yielding unbranched linear polymer materials with pendant sucrose moieties. Their physical properties indicate that these polymers have potential technological relevance as amphiphilic and biodegradable materials. Biodegradation tests on the copolymer samples by a fungal (Aspergillus niger) culture method showed a fungal growth ?60%, indicating good biodegradability and that the copolymers were partially bio-assimilated during microbial attack.     

Synthesis of new hybrid monomers and oligomers containing cationic and radical polymerizable vinyl groups and their photoinitiated polymerization

New hybrid vinyl monomers with both cationic- and radical-polymerizable vinyl groups were synthesized by the reaction of bis[1(chloromethyl)-2-(vinyloxy)ethyl]terephthalate ( 3 ) with unsaturated carboxylic acids using 1,8-diazabicyclo[5.4.0]-undecene-7 (DBU) as a base. The reaction of 3 with methacrylic acid 4a was carried out using DBU in DMSO at 70°C for 24 h to give an 86% yield of the hybrid vinyl monomer ( 5a ). Polycondensation of 3 with unsaturated dicarboxylic acids was also performed using DBU to give hybrid vinyl oligomers with radical polymerizable C (DOUBLE BOND) C groups (V_R) in the main chain and cationic polymerizable vinyl ether moieties (V_C) on the side chain. The photopolymerization of these hybrid vinyl compounds proceeded smoothly in bulk using either a cationic photoinitiator such as a sulfonium salt or a radical photoinitiator such as acyl phosphine oxide under UV irradiation. © 1996 John Wiley & Sons, Inc.     

Polymerization of coordinated monomers. XXII. Ab initio molecular orbital study on the binary radical complexes of 2-methoxycarbonyl propyl radical with boron trichloride and with boron trifluoride as a model of growing radical end

The geometrical and electronic structures of the binary radical complexes of 2-methoxycarbonyl propyl radical with boron trichloride and with boron trifluoride were determined by using an ab initio molecular orbital method. The 2-methoxycarbonyl propyl radical complex was a model of the growing radical end in the copolymerization of methyl methacrylate in the presence of boron halides. The most stable structure of the binary radical complex composed of 2-methoxycarbonyl propyl radical with boron trichloride was a twisted form in which the dihedral angle between the vinyl group and the ester group was 32°, while that of the binary radical complex composed of methyl methacrylate radical with boron trifluoride was a planar form as the free radical. The frontier orbital energy of 2-methoxycarbonyl propyl radical was lowered by 0.06 au by the coordination of boron trichloride, while that was lowered only by 0.02 au by the coordination of boron trifluoride. The polymerization mechanism was elucidated on the basis of these predictions. © 1993 John Wiley & Sons, Inc.