This review, including 245 references, describes the application of Lawesson's reagent [2,4-bis(p-methoxyphenyl)-1,3-dithiaphosphetane-2,4-disulfide] LR in organic and organometallic syntheses. Thionations of carbonyl-containing compounds as well as unexpected reactions are shown for different applications (e.g. cyclizations, rerrangements, syntheses of heterocyclic compounds etc.). Syntheses of novel organometallic compounds by LR are also discussed.

Polydisperse hyperbranched polyesters were modified for use as novel multifunctional reversible addition–fragmentation chain‐transfer (RAFT) agents. The polyester‐core‐based RAFT agents were subsequently employed to synthesize star polymers of n‐butyl acrylate and styrene with low polydispersity (polydispersity index < 1.3) in a living free‐radical process. Although the polyester‐core‐based RAFT agent mediated polymerization of n‐butyl acrylate displayed a linear evolution of the number‐average molecular weight (Mn) up to high monomer conversions (>70%) and molecular weights [Mn > 140,000 g mol−1, linear poly(methyl methacrylate) equivalents)], the corresponding styrene‐based system reached a maximum molecular weight at low conversions (≈30%, Mn = 45,500 g mol−1, linear polystyrene equivalents). The resulting star polymers were subsequently used as platforms for the preparation of star block copolymers of styrene and n‐butyl acrylate with a polyester core with low polydispersities (polydispersity index < 1.25). The generated polystyrene‐based star polymers were successfully cast into highly regular honeycomb‐structured microarrays. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3847–3861, 2003

The synthesis and characterization of novel first-and second-generation true dendritic reversible addition-fragmentation chain transfer (RAFT) agents carrying 6 or 12 pendant 3-benzylsulfanylthiocarbonylsulfanylpropionic acid RAFT end groups with Z-group architecture based on 1,1,1-hydroxyphenyl ethane and trimethylolpropane cores are described in detail. The multifunctional dendritic RAFT agents have been used to prepare star polymers of poly(butyl acrylate) (PBA) and polystyrene (PS) of narrow polydispersities (1.4 Ͻ polydispersity index Ͻ 1.1 for PBA and 1.5 Ͻ polydispersity index Ͻ 1.3 for PS) via bulk free-radical polymerization at 60°C. The novel dendrimer-based multifunctional RAFT agents effect an efficient living polymerization process, as evidenced by the linear evolution of the number-average molecular weight (M n ) with the monomer-polymer conversion, yielding star polymers with molecular weights of up to M n ϭ 160,000 g mol Ϫ1 for PBA (based on a linear PBA calibration) and up to M n ϭ 70,000 g mol Ϫ1 for PS (based on a linear PS calibration). A structural change in the chemical nature of the dendritic core (i.e., 1,1,1-hydroxyphenyl ethane vs trimethylolpropane) has no influence on the observed molecular weight distributions. The star-shaped structure of the generated polymers has been confirmed through the cleavage of the pendant arms off the core of the star-shaped polymeric materials.

Total synthesis concepts for the preparation of deoxygenated hexoses which are constituents of many secondary metabolites with antibacterial and antitumor activity are surveyed.