Copper-Catalyzed Three-Component Germyl Peroxidation of Alkenes

Abstract

The concurrent incorporation of a germyl fragment and another functional group (beyond the hydrogen atom) across the CC double bond is a highly appealing yet challenging task. Herein we demonstrate the efficient germyl peroxidation of alkenes with germanium hydrides and tert-butyl hydroperoxide via a copper-catalyzed three-component radical relay strategy. This protocol exhibits excellent functional group tolerance and exquisite chemo- and regioselectivity under mild conditions and represents a rare example of constructing synthetically challenging metal-embedded organic peroxides.

Organogermanium(iv) compounds in photo-induced radical reactions

“…Several transition metal-catalyzed methods for C-Ge bond formation have been reported. [25][26][27][28][29][30][31][32][33][34][35][36] Germatranes [37][38][39][40] and aryltriethylgermanes [41][42][43][44][45][46] have shown unique properties when applied as nucleophiles in Pd-or Au-catalyzed cross-coupling reactions. However, in visible-light photocatalytic systems, germanium compounds have not been widely used, till now.…”

Light‐Promoted Germylation of Aryl Propiolamides/Alkynoates: Synthesis of Ge‐Containing Spiro[4.5]trienones and Vinylgermanes

“…Due to its inherent sustainable properties, photocatalysis has attracted considerable attention and has been widely used for the construction of CÀ C and C-heteroatom bonds under mild reaction conditions. [15] In view of this and with our continuing interest in exploring germyl chemistry, [16] we reasoned that the germylation of the activated C�C triple bond could be coupled with tandem dearomative cyclization and/or 1,4-aryl migration to selectively generate the valuable germylcontaining spiro [4.5]trienones and/or vinylgermanes selectively. Based on this assumption, herein we would like to disclose the light-promoted regioselective difunctionalization of alkynes at room temperature without a transition-metal catalyst.…”

Regioselective Approach to β-Peroxyl Alcohols and Ethers from Alkenes

“…Among the already established protocols, difunctionalization of alkenes by installing a peroxide group and other different functional groups onto CC double bonds has been extensively studied and has proved to be a powerful tool in the formation of diverse peroxides. − In 2011, pioneering work on an Fe-catalyzed three-component carbonylation–peroxidation reaction of styrenes, hydroperoxides, and aldehydes was disclosed by Li and co-workers . Later, the three-component strategy became a powerful tool to realize the carbo-peroxidation of alkenes, silicon-peroxidation of alkenes, phosphate-peroxidation of alkenes, nitrogen-peroxidation of alkenes, iodine-peroxidation of alkenes, and thiolation–peroxidation of alkenes catalyzed by a metal or a Brønsted acid catalyst (Scheme a). Loh and co-workers reported an elegant work on direct coupling of the sp 3 α-carbon of alcohols with alkenes and hydroperoxides catalyzed by zerovalent copper- and cobalt-catalysts, generating a series of α-peroxy alcohol products (Scheme b) .…”

“…It is noteworthy that only recent studies have been able to afford α-peroxy products. − This may be attributed to the much slower reaction rate of the tert -butylperoxyl radical for its addition to alkenes via a radical process than that of other transient radicals . We hypothesized that looking for a radical which equips a much slower reaction rate than the tert -butylperoxyl radical would offer a different regioselective approach for the heteroatomic-peroxidation of alkenes.…”