Recent Advances in Cyclic Diacyl Peroxides: Reactivity and Selectivity Enhancement Brought by the Cyclic Structure

Abstract

Preliminarily studies on cyclic diacyl peroxides have shown novel and superior reactivities compared with their acyclic diacyl peroxide counterparts in many reaction types. After summarizing the methods available for the preparation of cyclic diacyl peroxides and describing their structural features, this review brings together an overview of their reactivities with respect to oxidations and decarboxylations, and demonstrates the advantages of reactions with cyclic diacyl peroxides, which include metal-free, additive-free, milder conditions, higher yields and better selectivities.1 Introduction2 Methods of Preparation of Cyclic Diacyl Peroxides3 Structures and Stabilities of Cyclic Diacyl Peroxides4 Oxidation Reactions4.1 Oxidative Additions to Alkenes4.2 Oxidation Reactions of Heteroatoms4.3 Oxidation Reactions of 1,3-Dicarbonyl Compounds4.4 Hydroxylations of Arenes5 Decarboxylations6 Conclusion

Sulfonamide-Directed Chemo- and Site-Selective Oxidative Halogenation/Amination Using Halogenating Reagents Generated in Situ from Cyclic Diacyl Peroxides

“…Inspired by the enzyme-catalyzed oxidative halogenation in nature and our continuing interest and efforts in the utilization of cyclic peroxides, we are intrigued by the possibility of complementing the existing Hofmann–Löffler–Freytag-type processes by the combination of cyclic diacyl peroxides and diverse halide salts. We speculated that such proposed halogenating reagents (Figure ) could increase the efficiency of Hofmann–Löffler–Freytag-type reactions by two potential pathways: increasing the reactivity of halogenating reagent by the existence of the intramolecular benzoates, or influencing the conformation of the substrates to favor reactivity and selectivity by intermolecular force.…”

Reductive Cleavage of Organic Peroxides by Iron Salts and Thiols

“…4,5 The same is true of peroxides activated by conjugation, stereoelectronics, or strain. 6 For example, ozonides (1,2,4-trioxolanes) are reduced by glutathione, 7 and we have demonstrated rapid inactivation of the enzyme papain by an ozonide-containing dipeptide analog. 8 Selenoperoxidases are able to reduce strained cyclic peroxides.…”

Syn-Dihydroxylation of Alkenes Using a Sterically Demanding Cyclic Diacyl Peroxide

“…Therefore, the synthesis and application of new peroxides with features that fulfill the above requirement remain a challenging task that must also take into account stability and safety. Additionally, simple manipulations of vicinal diacids as starting materials do not necessarily deliver the corresponding cyclic peroxides due to an inappropriate torsion angle or O–O bond distance as well as their inherent propensity for decarboxylation. , For instance, a phenyl group can readily be incorporated into P3 ; however, the resulting peroxide P5 is unstable and gradually decomposes at room temperature. The low stability of P5 could be attributed to the shortened O–O bond that increases the electrostatic repulsion of the peroxy oxygen lone pairs (Scheme ).…”

“…The low stability of P5 could be attributed to the shortened O–O bond that increases the electrostatic repulsion of the peroxy oxygen lone pairs (Scheme ). , Furthermore, the shortened O–O bond in P5 implies a higher conjugation between the carbonyl group and peroxy oxygen that increases its electron density. It was reported that the increase in the ring strain (CO–C–CO angles) of the peroxide directly translates into increased reactivity .…”

“…14a,b,16 Despite the great efforts made by Tomkinson and Siegel et al 14c for the metal-free syn-dihydroxylation of alkenes using established CAPs, there still remain some challenges concerning (1) the diastereoselectivities, (2) substrate scope, and (3) an asymmetric variant. Therefore, the synthesis and application of new peroxides with features that fulfill the above requirement remain a challenging task that must also take into 17,18 Furthermore, the shortened O−O bond in P5 implies a higher conjugation between the carbonyl group and peroxy oxygen that increases its electron density. It was reported that the increase in the ring strain (CO−C−CO angles) of the peroxide directly translates into increased reactivity.…”