A further application of TPPTS in catalysis: Efficient sucrose-butadiene telomerization using palladium catalysts in water

Sucrose-butadiene telomerization is efficiently carried out in water or water-organic medium in the presence of a palladium salt and TPPTS (TPPTS = trisodium tris(m-sulfonatophenyl)phosphine as catalyst. Mono- and dioctadienylether compounds are selectively obtained using a NaOH 1 M/isopropanol mixture.     

Controlled trans-stereospecific polymerization of isoprene with lanthanide(III) borohydride/dialkylmagnesium systems: The improvement of the activity and selectivity,kinetic studies,and mechanistic aspects

Neodymium trisborohydride, associated with MgR₂ alkylating agents, affords an efficient initiator for the stereospecific polymerization of isoprene. This system presents good activity (150 kg of polyisoprene/mol of Nd/h; 95% yield in 2 h) and is trans-stereospecific (up to 97.7%), and its polymerization shows a quasi-living character. The molecular weights are controlled by the [Isoprene]/[Nd] ratio, with a polydispersity index lower than 1.6. A full study is presented here, including the influence of the nature of the alkylating reagent (MgR₂), the solvent, the reaction temperature, the [MgR₂]/[Nd] ratio, and the replacement of neodymium by other lanthanides. This work also includes a kinetic study of the system and a detailed NMR study of the microstructure of the trans-polyisoprene obtained, providing mechanistic insights about the polymerization reaction. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2400–2409, 2007     

Borohydrido rare earth based coordinative chain transfer copolymerization: A convenient tool for tuning the microstructure of isoprene/styrene copolymers

A series of lanthanum and neodymium borohydrido complexes comprising the trisborohydrides Nd(BH₄)₃(THF)₃ ( 1a ) and La(BH₄)₃(THF)₃ ( 1b ) and the half‐lanthanidocenes Cp*Nd(BH₄)₂(THF)₂ ( 2a ) (Cp* = C₅Me₅) and Cp*La(BH₄)₂(THF)₂ ( 2b ) has been assessed for the chain transfer copolymerization of isoprene and styrene. A transmetalation process is occurring efficiently with the borohydride complexes in the presence of magnesium dialkyl. The transmetalation is accompanied by (i) a gradual decrease of the 1,4‐trans stereoselectivity of the reaction at the benefit of 3,4‐selectivity and (ii) an increase in the quantity of styrene inserted in the copolymer. This can be at least partially attributed to a magnesium induced co‐oligomerization of isoprene and styrene. By combining dialkylmagnesium and trialkylaluminum, a 1,4‐trans stereospecific reversible coordinative chain transfer copolymerization of isoprene and styrene is observed when the half‐lanthanocene 2b is used as precatalyst. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Chiral Ligands Derived from Monoterpenes: Application in the Synthesis of Optically Pure Secondary Alcohols via Asymmetric Catalysis

The preparation of optically pure secondary alcohols in the presence of catalysts based on chiral ligands derived from monoterpenes, such as pinenes, limonenes and carenes, is reviewed. A wide variety of these ligands has been synthesized and used in several catalytic reactions, including hydrogen transfer, C?C bond formation via addition of organozinc compounds to aldehydes, hydrosilylation, and oxazaborolidine reduction, leading to high activities and enantioselectivities.     

Ring‐opening polymerization of lactones using binaphthyl‐diyl hydrogen phosphate as organocatalyst and resulting monosaccharide functionalization of polylactones

Binaphthyl‐diyl hydrogen phosphate has been assessed for the first time as a catalyst for the ring‐opening polymerization of ε‐caprolactone (CL) and δ‐valerolactone (VL). In the presence of benzyl alcohol as coinitiator at 40–60 °C, the polymerization is quantitative and controlled both in terms of dispersity and of number‐average molecular weight corresponding to the monomer/initiator ratio. The use of a selectively protected D ‐glucose derivative bearing the primary C6 hydroxyl group as initiator leads to the quantitative end‐functionalization of the polyesters in rather short reaction times (ca. 10 min at 60 °C for δ‐VL) with dispersities around 1.08–1.10. Methyl‐α‐D ‐glucopyranoside has been used as a carbohydrate polyol initiator in bulk. The initiation efficiency is partial, leading to hydrophilic carbohydrates functionalized polylactones in a one‐step procedure. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

An acceleration property of theE-algorithm for alternate sequences

We prove a convergence acceleration result by theE-algorithm for sequences whose error has an asymptotic expansion on the scale of comparison for which a determinantal relation holds. This result is generalized to the vector case. Moreover we prove a result which contains an acceleration property for columns and diagonals of theE array. This result is applied to some alternating series.