Copper-Catalyzed Diastereoselective 1,2-Difunctionalization of Oxabenzonorbornadienes Leading to β-Thiocyanato Thioethers

Abstract

A novel copper-catalyzed complete diastereoselective 1,2-difunctionalization of oxabicyclic alkenes has been developed. Two C−S bonds were constructed simultaneously on the oxabenzonorbornadienes leading to βthiocyanato thioethers through the three-component (oxabicyclic alkenes, aryl iodides, and potassium thiocyanate), onepot reaction. Various functional groups attached to the substrates were tolerated in this protocol to afford the corresponding β-thiocyanato thioether products in moderate yields.

Transition-metal-catalyzed domino reactions of strained bicyclic alkenes

“…In 2019, the Yang lab examined the Cu-catalyzed diastereoselective 1,2-difunctionalization of oxabenzonorbornadienes 30 for the synthesis of β-thiocyanato thioethers 68 ( Scheme 12 ) [ 46 ]. In contrast to the previous difunctionalization reactions, the authors noted the reaction was stereoselective for the trans -addition product.…”

Recent progress of direct thiocyanation reactions

“…In 2019, Yang's research group reported a direct thiocyanation reaction using CuI as the catalyst. 10 In this method, the reaction of oxabenzonorbornadienes 1 , aryl iodides 2 and KSCN could construct two C–S bonds on the double bond simultaneously by a one-pot reaction, forming β-thiocyanato thioethers 3 . It is worth noting that the reaction is a stereoselective trans -addition and has good compatibility with a variety of substrates.…”

Recent Advances in Multicomponent Reactions with Organic and Inorganic Sulfur Compounds

“…A valuable and efficient copper‐catalyzed three‐component reaction of oxabicyclic alkenes 71 , aryl iodides, and potassium thiocyanate to synthesize corresponding β‐thiocyanato thioethers 73 was reported by Yang and co‐workers, [59] which was constructed two C−S bonds simultaneously. It provides a novel strategy for the use of potassium thiocyanate for sulfur‐containing molecules.…”