Organic Peroxides: Iii. Reactions of Dialkyl Peroxides With Organolithium and Organomagnesium Compounds

Abstract

Optinlum conditions for obtaining arylall;yl ethers from the reactions of aryl-lithium or -magnesium cornpot~nds with dialkyl peroxides have been investigated. The reactions arc considered to take place by ionic or four-center mechanis~ns.Gil~nan and Adams (I) found that, while di-(triphenylmethyl) peroxide is inert to phenylinagnesiulll bromide, diethyl peroxide reacts with it to give a 34% yield of phenetole. Di-t-butyl peroxide does not react with this Grignard reagent (2), even a t 80' (3), but reacts a t ordinary temperatures with the less-hindered Grignard reagents derived from primary and secondary bromides to give low yields of t-butyl ethers.Because of the possible usefulness of this method for synthesizing certain otherwise inaccessible ethers, we have studied the reactions of four dialkyl peroxides with phenyllithium and the pheilyl Grignard reagent (Table I), as well as the reactioil of dirnethyl peroxide with some other organo-lithiunl and -1nagnesiunl coinpounds (

Synthesis of Ethers via Reaction of Carbanions and Monoperoxyacetals

“…Spectral data matched those previously reported. 61 10-Phenyldecane Hydroperoxide (7). The title compound was prepared by an analogous strategy as described for hydroperoxides 4 and 6.…”

“… 5 The reaction of dialkyl peroxides with carbanions, while long known, 6 has largely remained a curiosity applied mainly to transfer of methoxyl and other unhindered alkoxides. 7 , 8 Even a slight increase in steric bulk results in reduced yields, 7 and reactions of di- t -butyl peroxide furnish multiple products. 9 , 10 We became interested in a general method for selective transfer of 1°, 2°, or 3° alkoxides from a mixed peroxide to a carbanion.…”

Oxacycle Synthesis via Intramolecular Reaction of Carbanions and Peroxides

“…Previous reports have described the intermolecular reaction of simple organometallics with dialkyl peroxides, 3 peresters, 4 and endoperoxides. 5 Bissilyl peroxides and lithiated hydroperoxides have been applied to oxygenation of lithiated arenes and alkenes.…”

General [4 + 1] Cyclization Approach To Access 2,2-Disubstituted Tetrahydrofurans Enabled by Electrophilic Bifunctional Peroxides

“…Conversely, the construction of such a bond from the corresponding carbon nucleophiles and the electrophilic oxygen center has been significantly underdeveloped . It has been long known that dialkyl peroxides could function as electrophilic oxygen sources to react with a stoichiometric amount of organometallic reagents such as Grignard reagents to furnish ether compounds, but the application of such an electrophilic alkoxylation strategy to the synthesis of oxygen heterocycles, for example, the tetrahydrofurans, was very rare. To the best of our knowledge, only one single example of using the reaction of cyclohexanone and tert -butyl iodopropyl peroxide 5a for the synthesis of spirotetrahydrofuran has been reported, by Dussault et al in 2014 .…”