Six-membered lodine lll Heterocycles

9 Polyq clic Heterocycles with an lodine(lll) Atom at a Ring Junction 

The first representatives of fused hypervalent iodine heterocycles with an iodine atom at a ring junction were described by Agosta in 1965 (1965TL2681). Compounds 200 and 201 were originally prepared by oxidation of the corresponding iodides 199 and 201 with peracetic acid 

The structures of products 203 (R = Bu ) (198 A3803) and 205 (2001JA1507) were determined by single-crystal X-ray analyses. Both structures have a distorted T-shape geometry arotmd the central iodine atom. The apical O—I—O bond angles of 203 and 205 are 144.5(1)° and 158.2(2)°, 

Iodosylarene 208 has high solubihty in organic solvents (up to 0.08 M in chloroform) and can be analyzed by NMR in solution (1999JA7164). A single-crystal X-ray analysis of compound 208 showed a pseudocycHc structure with an intramolecular distance of 2.707(5) A between one of 

Iminoiodane 209 has an excellent solubility in organic solvents (up to 0.14 M in chloroform at room temperature, at least a 50-fold increase over PhINTs). Compound 209 was analyzed by NMR in solution and by X-ray diffraction in the solid state. A single-crystal X-ray analysis of compound 209 demonstrated a pseudocyclic structure with an intramolecular distance of2.677(3)A between one of the sulfone oxygen atoms and the hypervalent iodine center (1999JA7164). Molecules of 209 are loosely associated into centrosymmetric dimers by long-range intermolecular I N and I 0 bonds (longer than 3.0 A), quite unlike the infinite polymeric chains adopted in the soHd state for PhINTs. 

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