91879-79-7Relevant academic research and scientific papers
Synthesis and crystal and molecular structure of μ-oxo-bis[trifluoroacetato(p-tolyl)iodine]
Chekhlov,Kasumov,Brel,Zefirov
, p. 800 - 806 (1996)
Crystal and molecular structure of μ-oxo-bis[trifluoroacetato(p-tolyl)iodine] (I) synthesized by a new procedure was determined by X-ray diffraction analysis. Crystals I are orthorhombic, unstable, space group Pbcn, a = 17.684(3), b = 8.453(3), c = 30.560(4) A, Z = 8. The structure of I was solved by direct and Fourier methods and refined by the full-matrix least-squares procedure in an anisotropic-isotropic approximation to R = 0.098 (CAD-4 automatic diffractometer, λCuKα, 1200 observed reflections with I ≥ 2σ). In molecule I, two iodine atoms have T-configuration of valence bonds with the average bond angles O-I-O 169(1) and O-I-C 86(2)°, average bond lengths I-Oμ 2.009(9), I-Oacet 2.269(9), and I-Caryl 2.11(1) A, and the bond angle I-O-1118.1(5)°. In molecule I, two p-Tol substituents are directed to approximately the same side of the medium plane of the central O-I-O-I-O fragment. Crystal structure I has I...O type intra- and intermolecular nonvalent interactions (secondary bonds). 1997 Plenum Publishing Corporation.
Efficient phenolic oxidations using μ-oxo-bridged phenyliodine trifluoroacetate
Dohi, Toshifumi,Uchiyama, Teruyoshi,Yamashita, Daisuke,Washimi, Naohiko,Kita, Yasuyuki
, p. 2212 - 2215 (2011)
The excellent oxidizing behavior of the μ-oxo-bridged phenyliodine trifluoroacetate 1 is revealed during the phenolic oxidations mediated by hypervalent iodine(III) reagents. The use of the μ-oxo-bridged compound 1 instead of PhI(OAc)2 (PIDA) a
Alternative Strategies with Iodine: Fast Access to Previously Inaccessible Iodine(III) Compounds
Hokamp, Tobias,Mollari, Leonardo,Wilkins, Lewis C.,Melen, Rebecca L.,Wirth, Thomas
supporting information, p. 8306 - 8309 (2018/06/29)
Non-iodinated arenes can be easily and selectively converted into (diacetoxyiodo)arenes in a single step under mild conditions by using iodine triacetates as reagents. The oxidative step is decoupled from the synthesis of hypervalent iodine(III) reagents, which can now be prepared conveniently in a one-pot synthesis for subsequent reactions without prior purification. The chemistry of iodine triacetates was also expanded to heteroatom ligand exchanges to form novel inorganic hypervalent iodine compounds.
Phenol and aniline oxidative coupling with alkenes by using hypervalent iodine dimer for the rapid access to dihydrobenzofurans and indolines
Dohi, Toshifumi,Toyoda, Yosuke,Nakae, Tomofumi,Koseki, Daichi,Kubo, Hiroko,Kamitanaka, Tohru,Kita, Yasuyuki
, p. 631 - 644 (2015/03/04)
A highly reactive hypervalent iodine dimer, [Ph(CF3COO)I]-O- [I(OCOCF3)Ph], is utilized as successful promoter in the oxidative phenolic coupling with styrenes leading to 2-aryldihydrobenzofurans. The extensions of the substrates in this study have led to the development of a new expeditious construction of the pyrroloindoline structure from aniline and enamide derivatives.
A concise synthetic route to the stereotetrad core of the briarane diterpenoids
Moon, Nicholas G.,Harned, Andrew M.
supporting information, p. 2218 - 2221 (2015/05/13)
A concise synthesis (under 10 steps) of the stereotetrad core of the briarane diterpenoids is reported. This approach harnesses the unique reactivity of salicylate ester derived 2,5-cyclohexadienones to quickly build complexity. In particular, a highly diastereoselective acetylide conjugate addition/β-ketoester alkylation sequence was used to set the relative configuration of the C1 (quaternary) and C10 (tertiary) vicinal stereocenters. The sterochemical outcome of the β-ketoester alkylation appears to be governed by torsional steering in the transition state.
Oxo-bridged Compounds of Iodine(III): Syntheses, Structure, and Properties of μ-Oxo-bis
Gallos, John,Varvoglis, Anastasios,Alcock, Nathaniel W.
, p. 757 - 764 (2007/10/02)
The title compound has been prepared by using several approaches.It reacts with both strong bases and acids and is an oxidant.Its crystal structure has been determined from four-circle diffractometer data (R=0.043).The primary iodine geometry is T-shaped o>, with shorter I-O (bridge) than I-O (acid) .Secondary bonds have I...O of 2.929(8) Angstroem to 3.273(8) Angstroem.
Conversion of Aliphatic Amides into Amines with benzene. 2. Kinetics and Mechanism
Boutin, Raymond H.,Loudon, G. Marc
, p. 4277 - 4284 (2007/10/02)
The reagent benzene (PIFA), used to prepare amines from amides as described in the preceding paper, dissolves in 50:50 (v/v) aqueous acetonitrile to give an acidic solution.This behavior can be explained quantitatively by the dimerization of PIFA in solution under preparatively significant conditions; the dimer, μ-oxo-I,I'-bis(trifluoroacetato-O)-I,I'-diphenyldiiodine(III), 2, can be isolated from the reaction mixture above pH 3.The rate of hexanamide rearrangement by PIFA was studied as a function of PIFA concentration and shown to display asymtotic behavior.The rate is depressed by added trifluoroacetate and accelerated by increasing pH, but not in a simple way.These observations can be accounted for by a mechanism (eq 13-15) in which the dimer 2 complexes with the amide, releasing acid.It is this released acid that accounts for most of the kinetically significant observations.The rearrangement of the amide-dimer complex is the rate-limiting step.Other kinetically indistinguishable mechanism are also possible.The rate of rearrangement promoted by dimer alone is in agreement with that predicted by the proposed mechanism.The imidic acid (enol) form of the amide is considered as a possible kinetically active form of the amide but is rejected on kinetic grounds.
