Synthetic Route to Enaminones via Metal-Free Four-Component Sequential Reactions of Aryl Olefins with CHCl₃, Et₃N, and TBHP

Abstract

An efficient and modular strategy was used to obtain enaminones with a wide range of functional groups via a four-component sequential reaction. This reaction proceeded under mild conditions without a catalyst in one pot. Furthermore, the products could be transformed into thiadiazoles.

Base-tuned selective 1,2-dichloromethylhydroxylation and 1,2-peroxyhydroxylation of 1,3-dienes via a tandem radical process

“…On the basis of the experiments mentioned above and previous literature, 9,11–14 we proposed a possible radical pathway for the formation of allyl alcohol 4a and 5a (Scheme 3). Initially, thermal homolysis of TBHP produces radicals ·OH I and t BuO· II with the aid of a base.…”

“…In recent years, our research group has been committed to studying the radical-mediated multi-component reactions of olefins, which starts from easily available starting materials and constructs multifunctional frameworks quickly. 9,10 Among them, some progress has been made in the olefin functionalization reaction involving chloroform. 9 We have synthesized α-tert-butylperoxide-β-dichloromethylalkanes, 9 a 1,1-dichloroalkanes, 9 b and enaminones 9 c by using TBHP as a radical initiator.…”

“…9,10 Among them, some progress has been made in the olefin functionalization reaction involving chloroform. 9 We have synthesized α-tert-butylperoxide-β-dichloromethylalkanes, 9 a 1,1-dichloroalkanes, 9 b and enaminones 9 c by using TBHP as a radical initiator. On the basis of the radical difunctionalization reaction of olefins in our group, we attempted the difunctionalization reaction of conjugated dienes mediated by TBHP.…”

TBHP Mediated C–N Bond Cleavage of Tertiary Amines toward the Synthesis of Oxalamides and α,β-Epoxy Amides

“…On the other hand, cleaving the highly stable C–N bond in tertiary amines and applying the fragments to construct new C–N or C–C bonds have aroused much attention. − However, previous investigations mainly focused on transition-metal catalysis processes. − In contrast, non-transition-metal catalysis for the activation of C–N bond has been rarely explored. Based on our previous work on β-ketoamides, herein, we present a simple and efficient protocol toward oxalamides by the reaction of β-ketoamides with tertiary amines via the tandem oxidation/amination process (Scheme d).…”

Cobalt-Catalyzed Oxyalkylation Reaction of Styrenes: Rapid Access to α-Alkyl Substituted Acetophenone Derivatives

“…However, there are drawbacks such as low yields or the usage of large amounts of peroxides in the reported methods. As a continuation of our research group's work on radical functionalization of olefin, [17][18][19][20][21] herein, we would like to describe a CoBr 2 -catalyzed oxyalkylation reactions of styrenes for the synthesis of α-alkyl substituted acetophenone derivatives (Scheme 1, b).…”