A practical synthesis of highly functionalized amines by the formal hydroamination reaction of alkenes with nitroarenes catalyzed by an air stable amine-bis(phenolate) iron(III) complex is reported. The reaction uses an easily handled silane, low catalyst loadings, and mild reaction conditions. A wide range of substrates are transformed with synthetically useful yields (21 examples).

The amine–bis(phenolate) iron(III)-catalysed reduction of ketones and aldehydes to the corresponding secondary and primary alcohols by a consecutive hydrosilylation/hydrolysis process is reported. The amine–bis(phenolate) iron(III) catalyst is easily accessible, stable towards moisture and air and has a broad substrate scope.

As the ubiquity and complexity of optical devices grows, our technology becomes more dependent on specialized functional materials. One area of continued interest is in high refractive index polymers as lightweight, processable and inexpensive alternatives to silicon and glass. In addition to a high refractive index, optical applications require these polymers to be transparent and have a low optical dispersion. Both nanocomposite and intrinsic high refractive index polymers offer particular advantages and disadvantages. While nanocomposite high refractive index polymers have refractive indices above 1.80, the nanoparticle type, content and size can negatively affect storage stability and processability. Alternatively, intrinsic high refractive index polymers are prepared by introducing an atom or substituent with a high molar refraction into a polymer chain; the resultant polymers are easier to store, transport, tune and process. Polymers containing aromatic groups, halogens (except fluorine), phosphorus, silicon, fullerenes and organometallic moieties have all shown significant promise. Many factors can affect intrinsic high refractive index polymer performance including molecular packing, molar volume, chain flexibility and substituent content. This mini-review summarizes the principles behind and recent developments in intrinsic high refractive index polymers. © 2014 Society of Chemical Industry

Aluminum-based salen and salan complexes mediate the ring-opening polymerization (ROP) of rac-β-butyrolactone (β-BL), rac-lactide, and ε-caprolactone. Al-salen and Al-salan complexes exhibit excellent control over the ROP of rac-β-butyrolactone, yielding atactic poly(3-hydroxybutyrate) (PHB) with narrow PDIs of <1.15 for Al-salen and <1.05 for Al-salan. Kinetic studies reveal pseudo-first-order polymerization kinetics and a linear relationship between molecular weight and percent conversion. These complexes also mediate the immortal ROP of rac-β-BL and rac-lactide, through the addition of excess benzyl alcohol of up to 50 mol eq., with excellent control observed. A novel methyl/adamantyl-substituted Al-salen system further improves control over the ROP of rac-lactide and rac-β-BL, yielding atactic PHB and highly isotactic poly(lactic acid) (P_m = 0.88). Control over the copolymerization of rac-lactide and rac-β-BL was also achieved, yielding poly(lactic acid)-co-poly(3-hydroxybutyrate) with narrow PDIs of <1.10. ¹H NMR spectra of the copolymers indicate a strong bias for the insertion of rac-lactide over rac-β-BL. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013