Dihaloiodoarenes: α,α-Dihalogenation of Phenylacetate Derivatives

A hypervalent iodine reagent-based α-carbonyl dihalogenation reaction is reported. Treating diazoacetate derivatives with either iodobenzene dichloride or iodotoluene difluoride results in <i>gem</i>-dichlorination or <i>gem</i>-difluorination products, respectively. The reaction is catalyzed by either Lewis acid or Lewis base activation of the aryl-λ³-iodane (ArIX₂) species and proceeds rapidly and chemoselectively to the desired <i>gem</i>-difunctionalized products in good to excellent yield

Iodide-Mediated Synthesis of Spirooxindolo Dihydrofurans from Iodonium Ylides and 3‑Alkylidene-2-oxindoles

An iodide-mediated reaction between cyclic iodonium ylides of 1,3-dicarbonyls and 3-alkylidene-2-oxindoles results in 3<i>H</i>-spiro­[furan-2,3′-indolin]-2′-ones. The reaction was tolerant to substitutions on both the alkylidene and ylide substrates and provided access to 19 new, densely functionalized polycyclic spirocycles in typically high yield

Iodide-Mediated Synthesis of Spirooxindolo Dihydrofurans from Iodonium Ylides and 3‑Alkylidene-2-oxindoles

An iodide-mediated reaction between cyclic iodonium ylides of 1,3-dicarbonyls and 3-alkylidene-2-oxindoles results in 3<i>H</i>-spiro­[furan-2,3′-indolin]-2′-ones. The reaction was tolerant to substitutions on both the alkylidene and ylide substrates and provided access to 19 new, densely functionalized polycyclic spirocycles in typically high yield

Wharton-Fragmentation-Based Approach to the Carbocyclic Core of the Phomoidrides

The carbocyclic core of the phomoidrides has been synthesized efficiently and in high yield. Key steps include a phenolic oxidation/intramolecular Diels–Alder sequence, tandem radical cyclization, and a late-stage Wharton fragmentation of a densely functionalized isotwistane skeleton