Alkene Oxyalkylation Enabled by Merging Rhenium Catalysis with Hypervalent Iodine(III) Reagents via Decarboxylation

Abstract

Rhenium-catalyzed oxyalkylation of alkenes is described, where hypervalent iodine(III) reagents derived from widely occurring aliphatic carboxylic acids were used as, for the first time, not only an oxygenation source but also an alkylation source via decarboxylation. The reaction also features a wide substrate scope, totally regiospecific difunctionalization, mild reaction conditions, and ready availability of both substrates. Mechanistic studies revealed a decarboxylation/radical-addition/cation-trapping cascade operating in the reaction.

Electrochemical Difunctionalization of Olefines: Access to Selenomethyl‐Substituted Cyclic Ethers or Lactones

“…[12] Generally, this process mainly focuses on transition metal catalysis (including Pd, [13] Ni, [14] Cu, [15] Ag, [16] Re, [17] Au, [18] Fe, [19] and others [20] ), metal-free catalysis (but requires [over-] stoichiometric amount of oxidants), [21] and photocatalysis. [12] Generally, this process mainly focuses on transition metal catalysis (including Pd, [13] Ni, [14] Cu, [15] Ag, [16] Re, [17] Au, [18] Fe, [19] and others [20] ), metal-free catalysis (but requires [over-] stoichiometric amount of oxidants), [21] and photocatalysis.…”

“…Currently, the difunctionalization of alkenes is a powerful and straightforward method for synthetizing various biologically active compounds and natural products. [12] Generally, this process mainly focuses on transition metal catalysis (including Pd, [13] Ni, [14] Cu, [15] Ag, [16] Re, [17] Au, [18] Fe, [19] and others [20] ), metal-free catalysis (but requires [over-] stoichiometric amount of oxidants), [21] and photocatalysis. [22] In recent years, electrochemical synthesis has attracted considerable attention in synthetic organic chemistry considering its utilization of electrons as "reagents" to accomplish the redox process; this process is a powerful tool for synthesizing organic compounds.…”

Iron‐Catalyzed Decarboxylative Alkyl Etherification of Vinylarenes with Aliphatic Acids as the Alkyl Source

“…We initiated our studies by screening the solvents used in the alkyl etherification reaction of styrene with lauroyl peroxide (LPO) in presence of Fe(OTf) 2 ( Table 1, entries [1][2][3][4][5][6][7][8]. Dioxane was found to be the most efficient solvent for this reaction and afforded the product in 69 %yield.…”

Copper‐Catalyzed 1,2‐Methoxy Methoxycarbonylation of Alkenes with Methyl Formate

“…In summary, methyl formate was successfully exploited for the first time in a synthetically useful Cu‐catalyzed difunctionalization of alkenes. Acting as a donor of both methoxycarbonyl and methoxy groups, methyl formate transforms styrene and its derivatives into value‐added β‐methoxy alkanoates and cinnamates, as well as medicinally important five‐membered heterocycles. It was believed that “the reaction of alkyl radicals is synthetically significant only when the olefinic double bond is conjugated with electron‐withdrawing groups owing to the nucleophilic character of the alkyl radical” .…”