Reactivity of hydroxy- and aquo(hydroxy)-λ3-iodane-crown ether complexes.

We have designed a series of hydroxy(aryl)-λ(3)-iodane-[18]crown-6 complexes, prepared from the corresponding iodosylbenzene derivatives and superacids in the presence of [18]crown-6, and have investigated their reactivities in aqueous media. These activated iodosylbenzene monomers are all non-hygroscopic shelf-storable reagents, but they maintain high oxidizing ability in water. The complexes are effective for the oxidation of phenols, sulfides, olefins, silyl enol ethers, and alkyl(trifluoro)borates under mild conditions.

The novel VEGF receptor/MET-targeted kinase inhibitor TAS-115 has marked in vivo antitumor properties and a favorable tolerability profile.

VEGF receptor (VEGFR) signaling plays a key role in tumor angiogenesis. Although some VEGFR signal-targeted drugs have been approved for clinical use, their utility is limited by associated toxicities or resistance to such therapy. To overcome these limitations, we developed TAS-115, a novel VEGFR and hepatocyte growth factor receptor (MET)-targeted kinase inhibitor with an improved safety profile.

Addition to electron deficient olefins of alpha-oxy carbon- centered radicals, generated from cyclic ethers and acetals by the reaction with alkylperoxy- lambda(3)-iodane.

Thermal decomposition of 1-tert-butylperoxy-1,2-benziodoxol-3(1H)-one in cyclic ethers and acetals at 50 degrees C generates alpha-oxy carbon-centered radicals, which undergo an addition reaction with vinyl sulfones and unsaturated esters.

Synthesis and characterization of beta-haloalkenyl-lambda3-bromanes: stereoselective Markovnikov addition of difluoro(aryl)-lambda3-bromane to terminal acetylenes.

Reported here for the first time are the synthesis, isolation, and characterization of hypervalent beta-haloalkenyl-lambda3-bromanes. Exposure of terminal alkynes to p-trifluoromethylphenyl(difluoro)-lambda3-bromane activated by BF3-i-Pr2O resulted in fluoro-lambda3-bromanation of the triple bonds in a Markovnikov fashion, yielding (E)-beta-fluoroalkenyl-lambda3-bromanes stereoselectively in good yields. 5-Chloro-1-pentynes undergo domino lambda3-bromanation-chlorine shift-fluorination or lambda3-bromanation-chlorine shift-alkyl shift-fluorination reaction, depending on the substituents and afford (E)-beta-chloroalkenyl-lambda3-bromanes stereoselectively in high yields.

Effects of complexation with 18-crown-6 on the hypernucleofugality of phenyl-lambda3-iodanyl groups. Synthesis of vinyl-lambda3-iodane.18-crown-6 complex.

[structure: see text] 4-tert-Butyl-1-cyclohexenyl(phenyl)(tetrafluoroborato)-lambda(3)-iodane forms a discrete supramolecular complex by the reaction with 18-crown-6. Solvolysis of the cyclohexenyl-lambda(3)-iodane in the presence of 18-crown-6 indicates that the complexation with 18-crown-6 tends to decrease the leaving group ability of hypervalent phenyl-lambda(3)-iodanyl groups.

Solid state structures of pentacoordinated lambda3-iodanes with a trigonal bipyramidal geometry: synthesis of diphenyl- and alkynyl(phenyl)-lambda3-iodane complexes with 1,10-phenanthroline.

The single crystal X-ray structure of the supramolecular complex formed between diphenyl-lambda3-iodane (Ph2IBF4) or 1-alkynyl(phenyl)-lambda3-iodane [Bu(t)CCI(Ph)BF4] and 1,10-phenanthroline indicates a hitherto unknown distorted trigonal bipyramidal geometry around iodine(III), in which 1,10-phenanthroline acts as a bidentate ligand and occupies equatorial sites.

Secondary hypervalent I(III)...O interactions: synthesis and structure of hypervalent complexes of diphenyl-lambda3-iodanes with 18-crown-6.

Reported here for the first time are the synthesis and characterization of supramolecular complexes between diaryl-lambda(3)-iodanes and 18-crown-6 (18C6). Slow evaporation of solvents afforded 1:1 and 2:1 complexes between Ph(2)IBF(4) and 18C6 as stable crystals, depending on the conditions. X-ray crystal structures of these complexes indicated that each iodine atom contacts with the three adjacent oxygen atoms of 18C6 through two hypervalent secondary bonding and a weak interaction.