Photochemical reactions, particularly those involving photoinduced electron transfer processes, establish a substantial contribution to the modern synthetic chemistry, and the polymer community has been increasingly interested in exploiting and developing novel photochemical strategies. These reactions are efficiently utilized in almost every aspect of macromolecular architecture synthesis, involving initiation, control of the reaction kinetics and molecular structures, functionalization, and decoration, etc. Merging with polymerization techniques, photochemistry has opened up new intriguing and powerful avenues for macromolecular synthesis. Construction of various polymers with incredibly complex structures and specific control over the chain topology, as well as providing the opportunity to manipulate the reaction course through spatiotemporal control, are one of the unique abilities of such photochemical reactions. This review paper provides a comprehensive account of the fundamentals and applications of photoinduced electron transfer reactions in polymer synthesis. Besides traditional photopolymerization methods, namely free radical and cationic polymerizations, step-growth polymerizations involving electron transfer processes are included. In addition, controlled radical polymerization and "Click Chemistry" methods have significantly evolved over the last few decades allowing access to narrow molecular weight distributions, efficient regulation of the molecular weight and the monomer sequence and incredibly complex architectures, and polymer modifications and surface patterning are covered. Potential applications including synthesis of block and graft copolymers, polymer-metal nanocomposites, various hybrid materials and bioconjugates, and sequence defined polymers through photoinduced electron transfer reactions are also investigated in detail.

In this Communication, the enantiomeric excess reported for the hydrogenation of N-(3,4-dihydronaphthalen-2-yl)acetamide was incorrect. An unnoticed impurity contained in the racemic sample led to the use of an inappropriate HPLC method for the determination of the optical purity. Reanalyzing the sample with a correct HPLC method (Chiralcel OD-H, hexanes/isopropyl alcohol (95:5), 1.0 mL min À1 , 210 nm, t(À) = 23.5 min, t(þ) = 27.5 min) [1] showed that the reduction product was obtained in only 9 % ee. The authors apologize for this error.

Conceptually new one-pot photoinduced sequential click reactions were implemented to yield novel block copolymers with the ability for cell adhesion. Poly(ε-caprolcatone) possessing clickable functional groups at the chain ends, namely α-alkynyl-ω-alkenyl-poly(ε-caprolactone) (A-PCL-MA), was prepared by ring-opening polymerization of ε-caprolactone using propargyl alcohol in the presence of stannous octoate at 110 °C followed by esterification with methacrylic acid. Azide-functional poly(methyl methacrylate) (PMMA-N3) was prepared independently by atom transfer radical polymerization (ATRP) followed by an azidation process using sodium azide. Finally, A-PCL-MA was reacted with PMMA-N3 and N-acetyl-l-cysteine (NAC) in a one-pot process through photoinduced sequential click reactions to furnish desired bioactive block copolymer (PMMA-b-PCL-NAC). A matrix for cell adhesion was then prepared from the yielded block copolymer PMMA-b-PCL-NAC and cell proliferation on the matrix was measured. Cells from the Vero cell line (African green monkey kidney epithelial) were incubated on the matrix, and after 48 h, they showed greater cell proliferation than the commercially available cell culture plates used as comparison.

In this work, we describe the use of the one-pot, photoinduced but photoinitiator-free combined copper-catalyzed azide-alkyne click cycloaddition (CuAAC) and atom-transfer radical polymerization (ATRP) protocol to provide a graft copolymer of polystyrene-g-poly(methyl methacrylate) (PS-g-PMMA) in desirable conversion and polydispersity. Poly(styrene-co-4-chloromethylstyrene) ( poly(S-co-4-CMS)) was prepared using nitroxide mediated polymerization (NMP). The benzylic chloride functional groups of poly(S-co-4-CMS) were substituted for azide functional groups using a conventional azidation procedure to provide poly(styrene-co-4-azidomethylstyrene) ( poly(S-co-4-AMS)). Poly(S-co-4-AMS) was then used as the backbone of the graft copolymer. The alkyne-bearing ATRP initiator propargyl 2-bromoisobutyrate (PgBiB) could then be grafted to the backbone via photoinduced CuAAC, while meanwhile initiating in tandem the poly(methyl methacrylate) (PMMA) chain growth via the ATRP mechanism. The graft polymer was provided in good conversion and polydispersity and was characterized appropriately using 1 H NMR, FT-IR and GPC.This journal is

MaxPHOS is an active and robust P-stereogenic ligand for asymmetric catalysis. The presence of an À NH À bridge between the two phosphine moieties allows the NH/PH tautomerism to take place. The neutral ligand, in which the NH form predominates, is an air-sensitive compound. However, protonation of MaxPHOS leads to the stable PH form of the ligand, in which the overall positive charge is distributed on both P centers. This protonation turns the MaxPHOS·HBF 4 salt 3 into an airstable compound both in the solid state and in solution.The salt 3 is also a convenient precursor for the preparation of rhodium(I) complexes by direct ligand exchange with the complexFinally, the corresponding rhodium(I)-MaxPHOS complex was tested in the asymmetric hydrogenation of a wide range of substrates. The complex proved to be a highly selective and robust system in these reactions.