Alkoxycarbonyloxy radicals

Isopropoxycarbonyloxy radicals undergo facile reaction with aromatic substrates (e.g. toluene) by reversible aromatic substitution. 94 Isopropoxycarbonyloxy radicals react with S to give ring substitution (ca 1%) as well as the expected double bond addition.40  

The chemistry of alkoxycarbonyloxy radicals in many ways parallels that of the aroyloxy radicals e.g. benzoyloxy, see 3.4.2.2.1). Products attributable to the reactions of alkoxy radicals generally arc not observed. Tltis indicates that the rate of p-.scission is slow relative to the rate of addition to monomers or other substrates.  

The alkoxycarbonyloxy radicals show little tendency to abstract 

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Changing the stmcture of R affects the activity of monoperoxycarbonates as previously discussed for peroxyesters. The other cogenerated radical is an alkoxycarbonyloxy radical. The nature of the R group has practically no effect on the reactivity of monoperoxycarbonates having the same 00-tert-55ky group. The 10-h half-life temperature remains at 100°C for almost ah. 00-tert-huty O-alkyl monoperoxycarbonates. 

Diall l Peroxydicarbonates. Some commercially available diaLkyl peroxydicarbonates and their corresponding 10-h half-life temperatures (deterrnined in trichloroethylene solutions) are Hsted in Table 7 (45). These peroxides are active at low temperatures and initially undergo homolytic cleavage to produce alkoxycarbonyloxy radical pairs that may subsequendy decarboxylate to produce alkoxy radicals ... 

Dialkyl peroxydicarbonates (21) undergo thermolysis to form two alkoxycarbonyloxy radicals that subsequentiy undergo -scission to form CO2 and alkoxy radicals ... 

Aroyloxy radicals are formed by thermal or photochemical decomposition of diaroyl peroxides (see 3.3.2.1) and aromatic peroxyesters (3.3.2.3) (Scheme 3.78) alkoxycarbonyloxy radicals are similarly produced from peroxydicarbonates (33.2.2). 

The alkoxycarbonyloxy radicals show little tendency to abstract hydrogen.188,431 For example, in the reaction of isopropoxycarbonyloxy radicals with MMA, hydrogen abstraction, while observed, is a minor pathway (<1%). When isopropoxycarbonyloxy radicals abstract hydrogen, isopropanol is the expected byproduct since the intermediate acid undergoes facile decarboxylation. Formation of isopropanol is not evidence for the involvement of isopropoxy radicals (Scheme 3.80). 

AA sec acrylic acid abstraction sec hydrogen atom transfer abstraction v,v addition and micleophilicity 35 by aikoxy radicals 34-5, 124-5, 392 by alkoxycarbonyloxy radicals 103,127-8 by alkyl radicals 34 5, 113, 116 by f-amyloxy radicals 124 by arenethiyl radicals 132 by aryl radicals 35, 118 by benzovloxy radicals 35, 53, 120, 126 wilh MM a" 53, 120 by /-butovy radicals 35, 53, 55, 124 solvent effects 54, 55. 123 with alkenes 122 3 with ally I acrylates 122 wilh AMS 120, 123 wilh BMA 53, 123 with isopropenvl acetate 121 with MA 120 with MAN 121 with MMA 53, 55, 120.419 with VAc 121 with vinyl ethers 123... 

Beckwith has observed moderate diastereoselectivity in this reaction involving cyclic systems. The cyclizations of allyl and homoallyloxycarbonyloxy radicals are potentially useful as radical based alternatives for an overall oxidation or hydrolysis of a double bond, and also various further transformations of the cyclic carbonates can lead to synthetically useful products.62b In contrast, simple alkoxycarbonyloxy radicals 91a add intermolecularly to ethyl vinyl ether to give, ultimately, carbonates of glycoaldehyde derivatives 91b, Scheme 37.62a... 

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