Stereoselective Cyclopropanation of (–)-Levoglucosenone Derivatives Using Sulfonium and Sulfoxonium Ylides

The synthesis of tri- and tetrasubstituted cyclopropanes from 3-aryl-substituted levoglucosenones (LGO) has been developed. In contrast to the unstabilised ylide dimethylsulfonium methylide which gives epoxides from LGO via 1,2-addition, we have found that the soft nucleophile dimethylsulfoxonium methylide affords cyclopropanes in moderate yields from LGO and in excellent yields and stereoselectivity with 3-aryl LGO derivatives. The use of 1,1,3,3-tetramethylguanidine as base in DMSO to generate the ylide provided the best yields and shortest reaction times. Ester stabilised sulfonium ylides could also be used to generate tetrasubstituted cyclopropane derivatives. One of the products was converted into a cyclopropyl lactone via Baeyer–Villiger oxidation to demonstrate the utility of applying cyclopropanation chemistry to LGO.

Well-defined triblock copolymers of polyethylene with polycaprolactone or polystyrene using a novel difunctional polyhomologation initiator

α,ω-Dihydroxy polyethylene, valuable precursor for the synthesis of polyethylene-based terpolymers with polar blocks, was synthesized by polyhomologation of dimethylsulfoxonium methylide with 9-thexyl-9-BBN, a novel difunctional initiator with two active and one blocked sites.

Well-defined 4-arm stars with hydroxy-terminated polyethylene, polyethylene-b-polycaprolactone and polyethylene-b-(polymethyl methacrylate)2 arms

Bis-boron-thexyl-silaboracycle was used to initiate the polyhomologation of dimethylsulfoxonium methylide to afford well-defined hydroxy-terminated 4-arm polyethylene (PE) stars, which served as precursors for the synthesis of PE-based starblock copolymers.