Copper-Catalyzed Borylative Methylation of Alkyl Iodides with CO as the C1 Source: Advantaged by Faster Reaction of CuH over CuBpin.

CuH and CuBpin are versatile catalysts and intermediates in organic chemistry. However, studies that involve both CuH and CuBpin in the same reaction is still rarely reported due to their high reactivity. Now, a study on CuH- and CuBpin-catalyzed borylative methylation of alkyl iodides with CO as the C1 source is reported. Various one carbon prolongated alkyl boranes (RCH2 Bpin and RCH(Bpin)2 ) were produced in moderate to good yields from the corresponding alkyl iodides (RI). In this cooperative system, CuH reacts with alkyl iodide faster than CuBpin.

Photocontrolled Iodine-Mediated Reversible-Deactivation Radical Polymerization: Solution Polymerization of Methacrylates by Irradiation with NIR LED Light.

Herein, near-infrared (NIR) photocontrolled iodide-mediated reversible-deactivation radical polymerization (RDRP) of methacrylates, without an external photocatalyst, was developed using an alkyl iodide (e.g., 2-iodo-2-methylpropionitrile) as the initiator at room temperature. This example is the first use of a series of special solvents containing carbonyl groups (e.g., 1,3-dimethyl-2-imidazolidinone) as both solvent and catalyst for photocontrolled RDRP using long-wavelength (λmax =730 nm) irradiation. The polymerization system comprises monomer, alkyl iodide initiator, and solvent. Well-defined polymers were synthesized with excellent control over the molecular weights and molecular weight distributions (Mw /Mn <1.21). The living features of this system were confirmed by polymerization kinetics, multiple controlled "on-off" light switching cycles, and chain extension experiments. Importantly, the polymerizations proceeded successfully with various barriers (pork skin and A4 paper), demonstrating the advantage of high-penetration NIR light.

Palladium-Initiated Radical Cascade Stereoselective Iodofluoroalkylation/Cycloisomerization of Ene-vinylidenecyclopropanes.

A novel and convenient palladium-initiated radical cascade stereoselective iodofluoroalkylation/cycloisomerization of ene-vinylidenecyclopropanes with fluoroalkyl iodides has been developed. The reaction proceeds under mild reaction conditions with high atom economy and stereoselectivity, thereby allowing an efficient access to a variety of difluoromethylated or perfluoroalkylated pyrrolidines tethered with an alkyl iodide. Two plausible radical pathways for the transformation have been proposed on the basis of the results of control experiments and previous reports, which in one case it was thought that palladium(0) was an initiator rather than a catalyst.

A straightforward one-pot two-step conversion of bile acids into dehomologated alcohols.

Irradiation of dichloroethane solutions of different bile acids with diacetoxy(iodobenzene) and iodine followed by treatment of the resulting raw mixture with MCPBA led to the 41-50% yields of the corresponding dehomologated alcohols in an uncomplicated one-pot protocol that can be completed in less than one day of work.