Lewis Acid Catalyzed Three‐Component Carbofunctionalization of Styrenes with Diacyl Peroxides and Nucleophiles

Abstract

A Lewis acid catalyzed carbofunctionalization of styrenes with diacyl peroxides and nucleophiles, including amines, indoles, trimethoxybenzenes, and carboxylic acid, has been accomplished. A wide range of primary, secondary, and tertiary alkyl diacyl peroxides generated from inexpensive aliphatic acids serve as both simple alkylating reagents and internal oxidants for the synthesis of value‐added amines, indoles, 1,1‐diarylalkanes, and esters in moderate to good yields. This protocol features site selectivity, broad substrate scope, and mild reaction conditions.

Creating, Preserving, and Directing Carboxylate Radicals in Ni-Catalyzed C(sp3)–H Acyloxylation of Ethers, Ketones, and Alkanes with Diacyl Peroxides

“…12,[25][26][27][28][29][30]51 The main problem is that in Ni-catalyzed processes, the initially formed O-centered acyloxy radicals undergo fast elimination of CO 2 , leading to C-centered radicals. 12,51,52 Since CO 2 formation is fast, 53 selective processes involving the acyloxy radical are challenging.…”

“…A suitable partner for such reactions could be diacyl peroxides, a readily available class of molecules used as radical initiators, oxidants, and sources of O- and C-functional groups. − Recently, cyclic diacyl peroxides − have emerged as O-electrophilic reagents for the introduction of oxygen functionalities into alkenes, − arenes, − heterocycles, and dicarbonyl compounds . However, despite this popularity, organic peroxides have not been documented as acyloxylation agents in Ni-catalyzed processes (Scheme A). ,− , The main problem is that in Ni-catalyzed processes, the initially formed O-centered acyloxy radicals undergo fast elimination of CO 2 , leading to C-centered radicals. ,, Since CO 2 formation is fast, selective processes involving the acyloxy radical are challenging.…”

Copper-Catalyzed Three-Component 1,5-Carboamination of Vinylcyclopropanes

“…Our group’s prior efforts focused on the development of Cu-catalyzed 1,2-carboamination of vinylarenes . While investigating this reaction, we used trans -1-phenyl-2-vinylcyclopropane as a mechanistic probe for radical intermediates (Scheme , A ): upon addition of the radical across the carbon–carbon double bond, the resulting radical adduct undergoes rapid ring opening followed by amination to afford a homoallylic amine. − Vinylcyclopropane (VCP) difunctionalization reactions are known to afford 1,5-products. Recent examples include, Wang’s copper-catalyzed 1,5-cyanotrifluoromethylation and Gutierrez’s iron-catalyzed 1,5-dicarbofunctionalization (Scheme , B ) .…”