Photocatalytic Decarboxylative Coupling of Aliphatic N‐Hydroxyphthalimide Esters with Bromopolyfluorobenzene

Abstract

We describe a decarboxylative coupling reaction of N‐hydroxyphthalimide esters with bromopolyfluorobenzene enabled by the synergetic action of Hantzsch ester, photoredox catalyst, and nickel catalyst. This method readily converts primary and secondary alkyl carboxylic acids into the corresponding polyfluoroaryl compounds with broad scope and excellent functional group compatibility. The practicality of this method was further demonstrated by the direct modification of amino acids and biologically active molecules

Synthesis of Heterodiarylmethanes via Metallaphotoredox Decarboxylative Arylation

“…6 The metallaphotoredox approach is appealing as it uses mild reaction conditions and commercially available catalysts. One drawback of many metallaphotoredox methodologies is the need for pre-functionalization of the alcohol or acid nucleophile into redox-active esters (e.g., xanthate 7a or NHP esters 7b c ), thereby adding an additional synthetic step. Moreover, a collaborative effort between the Doyle and the MacMillan groups has demonstrated the use of metallaphotoredox decarboxylative arylation to couple α-heteroatom carboxylic acids with (hetero)aryl halides, without the need for pre-functionalization (Scheme 1a ).…”

Nickel‐Catalysed Decarboxylative Coupling Reactions – An Overview

“…He et al put forward a protocol for the synthesis of essential polyfluoroaryl compounds 65 via Ni-catalysed coupling of bromopolyfluorobenzene 37 and N-Hydroxyphthalimide esters 2 in presence of Hantzsch ester and a photocatalyst. [40] Under the optimized condition, they investigated the scope of the reaction with regard to redox active esters, where cyclic and acyclic secondary alkyl substituted esters provided moderate to good yields (67-80 %) (Scheme 17). Electron-deficient, electronneutral and electron-rich aryl-substituted redox active esters also reacted successfully.…”

Highly Regio-/Stereoselective Synthesis of Carbohydrates with Unsaturated Glycosyl Donors under Mild Conditions

“…As most N-glycosides in nature are saturated, the unsaturated glycosides usually require dihydroxylation by OsO 4 . 47 After the establishment of the C-N glycosidic bonds between primary and secondar amines by palladium catalysis, K 2 OsO 4 •2H 2 O and NMO were directly added to the system for dihydroxylation reaction, so the deprotected glycosyl primary amine was originated by the one-pot method. The deprotected glycosides, with exposed hydroxyl groups, can exhibit higher biological activity.…”