Recent Advances in Radical Carbonylation

Sumino, Shuhei; Fukuyama, Takahide; Ryu, Ilhyong

doi:10.1002/9783527831883.ch12

Cited by 2 publications

(2 citation statements)

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“…Homoallylic radicals, arising from the cyclopropylcarbinyl radical ring opening, can trap CO to form acyl radicals. 26 27 The three-component coupling reaction comprised of alkylidenecyclopropanes, CO, and allylic bromides worked well to give good yields of 2-bromo-substituted 1,7-dien-5-ones (Scheme 10 ). For example, the treatment of a benzene solution of (1-butylpentylidene)cyclopropane, ethyl 2-(bromomethyl)acrylate, anhydrous trisodium phosphate, and V-65 with CO (80 atm) at 60 °C for 6 hours resulted in the production of ethyl 7-bromo-8-butyl-2-methylene-4-oxo-7-dodecenoate in 72% yield after purification by silica gel column chromatography.…”

Section: Synthesis Of 16-dienes By Bromoallylation Of Methylenecyclop...mentioning

confidence: 99%

Bromine-Radical-Mediated Bromoallylation of C–C Unsaturated Bonds: A Facile Access to 1,4-, 1,5-, 1,6-, and 1,7-Dienes and Related Compounds

Sumino

Ryu

2022

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The radical bromoallylation of alkynes, allenes, and vinylidene cyclopropanes proceeds efficiently in the presence of a radical initiator to give 2-bromo-substituted 1,4-, 1,5-, and 1,6-diene derivatives, respectively. Three-component reactions comprised of allenes, electron-deficient alkenes, and allyl bromides gives 1,7-dienes in good yields. The bromoallylation of an arylalkene can override the β-scission of the bromine radical from β-bromoalkyl radicals to give 5-bromoalkenes. The bromoallylation of vinylcyclopropanes is accompanied by 5-exo ring-closure to give 1-(bromomethyl)-2-vinylcyclopentane derivatives in good yields. All of the products contain a reactive vinyl-bromide moiety, which can be readily functionalized by Pd-catalyzed cross-coupling and radical cascade reactions.

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Section: Synthesis Of 16-dienes By Bromoallylation Of Methylenecyclop...mentioning

confidence: 99%

Bromine-Radical-Mediated Bromoallylation of C–C Unsaturated Bonds: A Facile Access to 1,4-, 1,5-, 1,6-, and 1,7-Dienes and Related Compounds

Sumino

Ryu

2022

Synlett

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“…2 CO has an important role in C1 chemistry owing to its high reactivity and its wide variety of reactive species available. 3 Transition-metal-catalyzed carbonylation reactions have provided vital methods for introducing CO into organic molecules, in which the migratory insertion of a CO ligand to a metal–carbon center takes place with the formation of an acyl-transition metal species, key precursors of carbonylated products. In contrast, the key step in radical carbonylation is simply the addition of carbon-centered radicals to CO with the formation of acyl radicals (Fig.…”

Section: Introductionmentioning

confidence: 99%