A novel, highly selective method for introducing organic sulfur, selenium, and tellurium functions into vinylic cyclopropanes has been developed on the basis of the relative reactivities of organic dichalcogenides and chalcogen-centered radicals. Upon irradiation with the light of wavelength over 300 nm, the reaction of vinylcyclopropanes with diphenyl disulfide and diphenyl diselenide proceeds smoothly to provide the corresponding gamma-(selenoethyl)allylic sulfides regioselectively in good yields. Similarly, vinylcyclopropanes undergo regioselective thiotelluration by use of a novel (PhS)(2)-(PhTe)(2) binary system, affording the corresponding ring-opened thiotelluration product in good yields. Furthermore, the scope and limitations of this (PhS)(2)-(PhTe)(2) binary system are discussed.

Amine-catalyzed, one-pot coproduction of dimethyl carbonate (DMC) and 1,2-diols from epoxides, methanol, and carbon dioxide has been reevaluated and investigated in detail. 1,8-Diazabicyclo-[5.4.0]undec-7-ene (DBU) serves as a desirable catalyst for the reaction. Heating of a mixture of glycidyl phenyl ether, methanol, a catalytic amount of DBU, and carbon dioxide at a total pressure of ca. 15 MPa at 150 °C gives DMC and the corresponding 1,2-diol in excellent yield (up to 97%). The influence of the reaction conditions on the DMC yield is discussed. The extension of this procedure to the synthesis of other symmetric dialkyl carbonates is also described.

Just the right strength of carbon‐radical trapping by diphenyl diselenide facilitates its selective three‐component coupling with an electron‐poor alkyne and an electron‐rich alkene [Eq. (1)]. In contrast, (PhS)2 is too weak and (PhTe)2 too strong a radical trap, and polymerization of the unsaturated compounds and addition of (PhTe)2 to the alkyne occur, respectively.

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