The direct, by-product–free conversion of basic feedstocks to products of medicinal and agricultural relevance is a broad goal of chemical research. Butadiene is a product of petroleum cracking and is produced on an enormous scale (about 12 × 106 metric tons annually). Here, with the use of a ruthenium catalyst modified by a chiral phosphate counterion, we report the direct redox-triggered carbon-carbon coupling of alcohols and butadiene to form products of carbonyl crotylation with high levels of anti-diastereoselectivity and enantioselectivity in the absence of stoichiometric by-products.

The ruthenium catalyst generated in situ from H2Ru(CO)(PPh3)3, (S)-SEGPHOS and a TADDOL-derived phosphoric acid promotes butadiene hydrohydroxyalkylation to form enantiomerically enriched products. Notably, the observed diastereo- and enantioselectivity is opposite of that observed using BINOL-derived phosphate counterions in combination with (S)-SEGPHOS, the same enantiomer of chiral ligand. Match-mismatch effects between chiral ligand and chiral TADDOL-phosphate counterion are described. For the first time, single crystal X-ray diffraction data is reported for a ruthenium complex modified by a chiral phosphate counterion.

The ruthenium catalyst derived from Ru3(CO)12 and triphos [Ph2P(CH2CH2PPh2)2] promotes the direct C–C coupling of isoprene with aryl substituted hydantoins 1a–1f at the diene C4-position to furnish products of n-prenylation 2a–2f. A mechanism involving hydantoin dehydrogenation followed by diene-imine oxidative coupling to furnish a transient aza-ruthencyclopentene is proposed.

The direct approach: Ruthenium(0)‐catalyzed hydrohydroxyalkylation of α‐olefins and styrenes with 3‐hydroxy‐2‐oxindoles forms branched products of CC coupling with high levels of diastereocontrol. A mechanism involving diene–olefin oxidative coupling and a subsequent carboxylic acid co‐catalyzed transfer hydrogenolysis of the resulting oxaruthenacycle intermediate is postulated.

Anionic polymerizations of acrylates possessing 1‐pyrenyl (Py1), 1‐naphthyl (Np1), 2‐naphthyl (Np2), and 2‐fluorenyl (Fl2) groups as α‐substituents were investigated as well as the properties of the obtained polymers. Py1 and Np1 did not undergo polymerization, whereas Np2 and Fl2, annulated α‐phenylacrylates at 3,4‐position of the phenyl group, afforded homo‐oligomers and alternating copolymers with methyl methacrylate (MMA). The oligomer of Fl2 [oligo(Fl2)] exhibited strong excimer emission in diluted solution. In contrast, dominant monomer emission was observed for the alternating copolymer with MMA [poly(Fl2‐co‐MMA)]. In the alternating copolymer, MMA units could function as spacers preventing the association of pendant fluorene moieties to suppress the excimer formation. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 2806–2814