ConspectusThe chemistry of hypervalent iodine(III) compounds has gained great interest over the past 30 years. Hypervalent iodine(III) compounds show valuable ionic reactivity due to their high electrophilicity but also express radical reactivity as single electron oxidants for carbon and heteroatom radical generation. Looking at ionic chemistry, these iodine(III) reagents can act as electrophiles to efficiently construct C–CF3, X–CF3 (X = heteroatom), C–Rf (Rf = perfluoroalkyl), X–Rf, C–N3, C–CN, S–CN, and C–X bonds. In some cases, a Lewis or a Bronsted acid is necessary to increase their electrophilicity. In these transformations, the iodine(III) compounds react as formal “CF3+”, “Rf+”, “N3+”, “Ar+”, “CN+”, and “X+” equivalents. On the other hand, one electron reduction of the I(III) reagents opens the door to the radical world, which is the topic of this Account that focuses on radical reactivity of hypervalent iodine(III) compounds such as the Togni reagent, Zhdankin reagent, diaryliodonium salts, ary...

Iodine(III) Reagents in Radical Chemistry

Chemical transformations induced by hypervalent iodine reagents

Fluoroalcohols: versatile solvents in hypervalent iodine chemistry and syntheses of diaryliodonium(III) salts

Hypervalent iodine(III): selective and efficient single-electron-transfer (SET) oxidizing agent

Modern methods for the synthesis of substituted naphthalenes

Novel and direct nucleophilic sulfenylation and thiocyanation of phenol ethers using a hypervalent iodine(iii) reagent

An Efficient Synthesis of peri-Hydroxy Aromatic Compounds: A Strong Base-Induced [4 + 2]Cycloaddition of 4-Phenylthio-Substituted Homophthalic Anhydrides with Various Sulfinyl-Substituted Dienophiles

A direct and regioselective synthesis of p-phenylthio-substituted peri-hydroxy polyaromatic compounds (9–12) was developed via the strong-base-induced [4+2] cycloaddition of the 4(phenylthio)homophthalic anhydrides (1a–d) to the phenylsulfinyl-substituted dienophiles (5–8). The sulfinyl group in 5–8 is the key to producing the desired reaction under mild conditions (at – 20 °C to room temperature) in good yields. A reaction mechanism explaining the remarkable effect of the sulfinyl group is discussed.

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Synthesis of p-phenylthio- peri-hydroxy polyaromatic compounds by strong-base-induced [4+2] cycloaddition of 4-(phenylthio)homophthalic anhydrides with phenylsulfinyl- dienophiles

Novel and Direct Nucleophilic Sulfenylation and Thiocyanation of Phenol Ethers Using a Hypervalent Iodine(III) Reagent.

An Efficient Synthesis of peri-Hydroxy Aromatic Compounds: A Strong Base-Induced [4 + 2] Cycloaddition of 4-Phenylthio-Substituted Homophthalic Anhydrides with Various Sulfinyl-Substituted Dienophiles.

Brendan A. Whelan

Papers

Novel and direct nucleophilic sulfenylation and thiocyanation of phenol ethers using a hypervalent iodine(iii) reagent

An Efficient Synthesis of peri-Hydroxy Aromatic Compounds: A Strong Base-Induced [4 + 2]Cycloaddition of 4-Phenylthio-Substituted Homophthalic Anhydrides with Various Sulfinyl-Substituted Dienophiles

Synthesis of p-phenylthio- peri-hydroxy polyaromatic compounds by strong-base-induced [4+2] cycloaddition of 4-(phenylthio)homophthalic anhydrides with phenylsulfinyl- dienophiles

Novel and Direct Nucleophilic Sulfenylation and Thiocyanation of Phenol Ethers Using a Hypervalent Iodine(III) Reagent.

An Efficient Synthesis of peri-Hydroxy Aromatic Compounds: A Strong Base-Induced [4 + 2] Cycloaddition of 4-Phenylthio-Substituted Homophthalic Anhydrides with Various Sulfinyl-Substituted Dienophiles.