氟烷基化与氟烷氧基化的研究——25.甲酸/三乙胺引发氟烷基碘对烯烃的加成

氟烷基碘对烯烃的催化加成,是将氟烷基引入碳氢化合物的有效途径。通常利用光照和自由基引发来实现。最近我们发现许多金属     

On Thermodynamic Characteristics of In–I System Compounds

The temperature dependences of the total vapour pressure for solid and liquid InI₂ and liquid InI₃ were measured by the static method with a membran‐gauge manometer. The heat capacities above phases and solid InI₃ were also obtained. The partial pressures In₂I₆, InI₃, InI, In₂I₄, I₂, I were calculated. Absolute entropies and enthalpies of formation InI₂ (crII), InI₂ (l), In₂I₄ (g), InI₃ (l), InI₃ (g), In₂I₆ (g) were obtained. We used the least square method to obtain the mutual consistent sets of data on thermodynamic characteristics of indium iodides in condensed and gaseous phases. The result of this work is the set of standard formation enthalpies and absolute entropies of the In–I system compounds.     

Practical and efficient synthesis of perfluoroalkyl iodides from perfluoroalkyl chlorides via modified sulfinatodehalogenation

A novel two-step one pot synthesis of perfluoroalkyl iodides (α,ω-diiodoperfluoroalkanes) from perfluoroalkyl chlorides (α-chloro-ω-iodoperfluoroalkanes) has been developed by initial conversion to the corresponding sodium perfluoroalkanesulfinates with sodium dithionite and then subsequent oxidation by iodine.     

Regiocontrolled synthesis of highly-functionalized fused imidazoles: a novel synthesis of second generation LFA-1 inhibitors

A new and reliable route to a new class of LFA-1 inhibitors such as (2) has been developed. A key aspect of this route is the transformation of amino amide 5 into iodide 3 in four steps. Iodide 3 is a key advanced intermediate used in the synthesis of all second-generation 1H-imidazo[1,2-α]imidazol-2-one LFA-1 inhibitors.     

Copper-mediated direct arylation of benzoazoles with aryl iodides

The direct arylation of 1,3-benzoazole compounds with aryl iodides is effectively promoted by CuI with use of PPh₃ and Na₂CO₃ or K₃PO₄ as ligand and base, respectively, in DMF or DMSO to produce the corresponding 2-arylated products with good yields.     

Efficient and direct synthesis of saccharidic 1,2-ethylidenes, orthoesters, and glycals from peracetylated sugars via the in situ generation of glycosyl iodides with I2/Et3SiH

Peracetylated sugars can be efficiently converted into the corresponding 1,2-ethylidenes, -orthoesters, and -glycals via the in situ generation of glycosyl iodides promoted by I₂/Et₃SiH. The approach is straightforward and avoids isolation of the sensitive iodinated intermediates.     

Copper catalyzed arylation of urea

An efficient copper catalyzed amidation of aryl iodides with urea is described. This method is milder than the palladium catalyzed arylation and avoids the use of toxic phosphine ligands.     

New electrophilic iodochlorinating systems based on iodine (+1)

Two new convenient systems for electrophilic iodochlorination of olefins are proposed: KIO₃+I₂+HCl (in aqueous solutions) and KlCl₄+I₂ (in organic solvents). Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 877–878, April, 1997.     

三元二价稀土碘化物的一步合成及其性质和结构

报道了合成三元二价稀土碘化物的新方法,其优点是操作方便、省时,并避免事先合成易氧化吸水的REI_3或REI_2,特别是当某些稀土元素同时生成二价与三价稀土碘化物而不易分离时,此法最有效,用此法合成了RbTmI_3、KTmI_3、Cs_2mI_4、TISm_2I_5、K_2SmI_5和KSm_2I_4,并测定了它们的性质与结构。     

Synthesis,characterization, and crystal structures of iodides and polyiodides of scandium complexes with urea and acetamide

Iodides and polyiodides of scandium complexes containing urea (Ur) and acetamide (AA) have been synthesized and characterized by elemental analysis, IR spectroscopy, and X-ray diffraction. The trigonal crystals of [Sc(L)₆]I₃ (L?=?Ur, AA) and monoclinic crystals of [Sc(Ur)₆][I₃]₃ are isomorphous to the earlier reported [M(Ur)₆]I₃ (M?=?Ti, V, Cr, Fe) and [Ln(Ur)₆][I₃]₃ (Ln?=?Yb, Lu), respectively. Therefore, scandium in its complexes with urea and iodine links rows of 3d transition elements and rare-earth elements; it continues the tendency of formation of polyiodides with different structures from isomorphous iodides, which was found for other metal(III) urea complexes. In the orthorhombic crystals of [Sc(AA)₆][I₅][I₃]I, the first example of the M(III) acetamide polyiodide, metal ions in complex cations are located at the centers of distorted octahedral arrangements of oxygen atoms of acetamide; iodide ions are not coordinated. The crystals of [Sc(AA)₆][I₅][I₃]I contain V-shaped pentaiodide, linear triiodide, and isolated iodide anions.     

Unexpected Transformation of Aldehydes into Benzoins with Copper(I)/Samarium

The reductive coupling of aldehydes to afford pinacolic alcohols using all kinds of reducing agents involving samarium is well known. In this report, however, treatment of aromatic aldehydes with Cu(I)/Sm system produces benoins and/or benzils in good yields. A possible mechanism is proposed where Cu(I) not only activates the Sm metal but also promotes the dehydrogenation of the intermediates, during which a Cu(III) species may be involved.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]     

A two-step approach to 2-polyfluoroalkyl quinolines from N-aryl polyfluoroalkyl imidoyl iodides

2-Polyfluoroalkyl quinoline derivatives were synthesized from the enaminones which were obtained from the reaction of N-aryl polyfluoroalkyl imidoyl iodides with methyl ketones.     

Solvent‐Free Iodination of Arenes using Iodine–Silver Nitrate Combination

A simple and environmentally safe general method of iodination of aromatic substrates under sovent‐free conditions using the I₂/AgNO₃ combination in a solid state is reported. Both activated and deactivated aromatic compounds afford the respective aryl iodides in generally high yields (80–90%).     

可见光诱导烯烃串联加成环化合成多氟烷基化异喹啉二酮

发展了一种可见光诱导的活泼烯烃与全氟碘代烷串联加成环化合成多氟异喹啉二酮的反应。 在可见光诱导下,多种N-丙烯酰基-N-丁基苯甲酰胺衍生物与全氟碘代烷发生自由基串联加成环化反应,以54%~80%的产率合成了一系列的多氟取代异喹啉二酮衍生物。 为具有潜在药用价值的多氟取代异喹啉二酮合成提供了一条高效、条件温和、绿色的新途径。     

Palladium‐Initiated Radical Cascade Stereoselective Iodofluoroalkylation/Cycloisomerization of Ene‐vinylidenecyclopropanes

A novel and convenient palladium‐initiated radical cascade stereoselective iodofluoroalkylation/cycloisomerization of ene‐vinylidenecyclopropanes with fluoroalkyl iodides has been developed. The reaction proceeds under mild reaction conditions with high atom economy and stereoselectivity, thereby allowing an efficient access to a variety of difluoromethylated or perfluoroalkylated pyrrolidines tethered with an alkyl iodide. Two plausible radical pathways for the transformation have been proposed on the basis of the results of control experiments and previous reports, which in one case it was thought that palladium(0) was an initiator rather than a catalyst.     

Studies on ABX6 Compounds. IV. The structures of AUI6 compounds (A: Sr,Eu, Ba)

The compounds SrUI₆, EuUI₆ and BaUl₆ are synthesized for the first time. Their crystal structures are isotypic, and they can be described as ordered substitution variants of the AlCl₃ type.     

Palladium-catalyzed phenyl-selenylation with n-Bu3SnSePh in one-pot two-step reactions

We have studied the Pd-catalyzed cross-coupling reaction of a stannane derived from selenium n-Bu₃SnSePh (1) with aryl and perfluoroalkyl iodides. Herein a very efficient one-pot two-step selenylation reaction to form a C-Se bond is reported. Ph₂Se₂ reacts with Na metal in liquid ammonia yielding PhSe⁻ ions. To this solution n-Bu₃SnCl was added to afford 1, which was introduced in the palladium-catalyzed coupling reaction without isolation. These reactions afford functionalized diarylselenides and phenylperfluroalkyl selenides from good to high yields (38-98%).     

Studies on ABX6 Compounds. V. Thermodynamics and kinetics of the high pressure transformations on ABX6 compounds (A = Ca,Dy, Ge,Sn, Pb; B = Th,U; X = I)

The results of high pressure experiments with ternary iodides of the general formula ABI₆ with A = Ca, Dy, Ge, Sn, Pb and B = Th, U are described. These compounds transform from a β- to a γ-SnThI₆-type structure, both variants of known trihalide structures (BiI₃- and PuBr₃-type). Trends and pecularities in the values for the minimal transformation pressures and in the velocities of transition are pointed out, and they are discussed in terms of geometric and electronic factors.     

Facile synthesis of phenacyl iodides from styrenes under visible light irradiation with fluorescent lamps

Phenacyl iodides were easily synthesized from styrenes with iodine under irradiation of visible light from a fluorescent lamp.     

Copper-and Silver-Mediated Cyanation of Aryl Iodides Using DDQ as Cyanide Source

A new copper and silver‐mediated cyanation of aryl iodides with DDQ as a cyanide source is achieved, providing nitriles with good yields. This new approach represents a safe method leading to aryl nitriles.