Addition of Per(poly)fluoroalkyl Iodides to vinyl Cyclopropane Derivatives: Synthesis of Fluoroalkyl Substituted γ,δ-Unsaturated Carbonyl Compounds

In the presence of CrC13 /Fe bimetal couple,per(poly)fluoroalkyl iodides add to vinyl cyclopropane compounds giving addition-ring-opening products in good yields.

STUDIES ON POLYHALOALKANES Ⅳ. THE REACTION OF POLYFLUOROALKYL IODIDES WITH SILVER(I) SALTS

The conversion of polyfluoroalkyl iodides into the corresponding carboxylic acids by the reaction with silver (I) salts is described.

A SIMPLE ACCESS TO UNSOLVATED MONOMERIC COMPLEXES OF EARLY LANTHANIDE IODIDES(CH_3OCH_2CH_2C_5H_4)_2LnI(Ln=La,Nd)VIA THE REACTION OF[(CH_3OCH_2CH_2C_5H_4)_2LnCl]_2 WITH NaI AND X-RAY CRYSTAL STRUCTURE OF THE LANTHANUM COMPLEX

(CH_3OCH_2CH_2C_5H_4)_2LnI(Ln=La,Nd)complexes have been synthesized by the reaction between NaI and[(CH_3OCH_2CH_2C_5H_4)_2LnCl]2 in THF;A single crystal X-ray study has shown that the lanthanum complex is an unsolvated monomer with lanthanum(Ⅲ)in a trigonal bipyramidal coordination geometry if the cyclopentadienyl ring is regarded as occupying a single polyhedral vertex.

STUDY ON Cp_2TiCl_2/Fe-INITIATED ADDITION OF 2-HALOTETRAFLUOROETHYL IODIDES TO ALKYNES AND ALKENES

Initiated by CP_2TiCl_2/Fe redox system,2-halotetrafluoroethyl iodides readily reacted with alkynes or alkenes to give 1:1 adducts in good to excellent yields.

ORGANOPHOSPHINE INITIATED REACTION OF PERFLUOROALKYL IODIDES WITH ALKENES

perfluoroalkyl iodides reacted with alkenes in acetonitrile solu- tion containing catalytic amount of organophosphine under mild condition to give the corresponding adducts in moderate to good yields.Reaction was shown to involve a free radical mechanism.

Copper-mediated 1,4-conjugation reaction of functionalized alkylzinc iodides with derivatives of β-nitrostyrene

Functionalized alkylzinc iodides will undergo 1,4-conjugation reaction with derivatives of β-nitrostyrene in the presence of Cu(OAc)2/LiCl to afford a polyfunctional nitro-compound in high yield.

CuI-catalyzed Synthesis of Aryl Thiocyanates from Aryl Iodides

An operationally simple and inexpensive catalyst system was developed for the cross coupling of potassium thiocyanate with aryl iodides by using CuI as catalyst, 1, 10-phenanthroline as ligand, and tetraethylammonium iodide as activator. The procedure is applicable for the synthesis of diverse aryl thiocyanates without any exotic, poisonous reagents.

Remarkable rate acceleration of SmI3-mediated iodination of acetates of Baylis-Hillman adducts in ionic liquid: facile synthesis of (Z)-allyl iodides

Stereoselective transformation of Baylis-Hillman acetates I into corresponding （Z）-allyl iodides 2 has been achieved by treatment of I with samarium triiodide in THF. Remarkable rate acceleration of samarium triiodide-mediated iodination of 1 was found when ionic liquid 1-n-butyl-3-methyl-imidazolium tetrafluroborate （[bmim]BF4） was used as reaction media in stead of THF. This novel approach proceeds readily at 50 ℃ within a few minutes to afford （Z）-allyl iodides 2 in excellent yields. A mechanism involving stereoselective iodination of the acetates of Baylis-Hillman adducts by samarium triiodide is described, in which a six-membered ring transition state played a key role in the stereoselective formation of 2.

Solid-phase synthesis of (Z)-allyl iodides from 3-acetoxy-2-methylene-alkanoates with recyclable polymer-supported selenium bromide

Reaction of polystyrene-supported lithium selenide with 3-acetoxy-2-methylene-alkanoates afforded the corresponding allyl selenide resins and subsequent cleavage from the polymer by treating with methyl iodide to furnish （Z）-allyl iodides in good yields and high purities. The polymeric selenium reagent can be regenerated and reused. So it is a environmentally benign reagent.

Electrochemical Radical Borylation of Aryl Iodides

Herein,we report the first electrochemical strategy for the borylation of aryl iodides via a radical pathway using current as a driving force.A mild reaction condition allows an assorted range of readily available aryl iodides to be proficiently converted into synthetically valuable arylboronic esters under transition metal catalyst-free conditions.Moreover,this method also shows good functional group tolerance.Initial control mechanistic experiments reveal the formation of aryl radical as a key intermediate and the current plays an important role in the generation of radical intermediate.

Synthesis of alkynes and alkynyl iodides bearing a protected amino alcohol moiety as functionalized amino acids precursors

Amino acid precursors in protected amino alcohol form are important synthons that can be used as building-blocks for the hemisynthesis of non-natural amino acids.Serine can be used as a common starting material for the synthesis of such compounds differently protected.Particularly,protected amino alcohols bearing an ethynyl and/or an iodoethynyl group can be used in cross-couplings,in 1,3-dipolar cycloadditions and/or in Nozaki-Hiyama-Kishi type reactions.We thus demonstrated that the efficiently protected amino alcohols derived from serine can be coupled to a sugar derivative by an indium mediated alkynylation reaction.The conditions of this coupling are compatible with such functionalized derivatives and allow envisaging an access to C-glycosylated amino acids.

Tetrazole-1-acetic acid as a ligand for copper-catalyzed N-arylation of imidazoles with aryl iodides under mild conditions

Tetrazole-l-acetic acid was found to serve as a superior ligand for Cul-catalyzed N-arylation of imidazoles with aryl iodides under a low catalyst loading （5 mol% of Cul）. A variety of aryl iodides could he aminated to provide the N-arylated products in good to excellent yields without the need of an inert atmosphere.

Study of Divalent Rare Earth Iodides

Properties of trivalent rare earth ions have been extensively understood. Besidesthe +3 valent state, the rare earth elements also have +4, +2 and +1 valencies,clusters and mixture valent compounds. The research of their synthesis, structure,properties of unusual valent rare earth compounds has theoretical and practicalsignificance. It will broaden the horizon of rare earth chemistry and extend

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, provid- ing nitriles with good yields. This new approach represents a safe method leading to aryl nitriles.

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 FT-aryl polyfluoroalkyl imidoyl iodides with methyl ketones.

Studies on polyhaloalkanes Ⅰ.Radical addition of polyfluoroalkyl iodides to diethyl allylphosphonate

Radical addition of polyfluoroalkyl iodides to the C=C double bond of diethyl allylphos- phonate was carried out in CH_2Cl_2-H_2O two-phase medium in the presence of sodium dithionite to give dicthyl 3-polyfluoroalkyl-2-iodopropylphosphonates(3)in excellent yields.Compounds 3 were then converted to diethyl polyfluoroalkanephosphonates(4)by zinc-reduction,Thus a facile method for preparing polyfluoroalkanephosphonates is realized.

Studies on sulfinatodehalogenation——XVIII. The reaction of perfluoroalkyl iodides with α-methylene cyclic ethers

Perfluoroalkyl iodides reacted with various a-methylene oxacycloalkanes in the presence of sodium dithionite to give ring opening adducts. The reaction provided an efficient method for the syntheses of polyfunctional organofluorine compounds.

Homocoupling of Aryl Iodides Catalyzed by Cyclopalladated Complexes of Tertiary Arylamines

Homocoupling of aryl iodides catalyzed by cyclopalladated complexes of tertiary arylamines gives symmetric biaryls with good yields in DMA or ionic liquid [Bmim]BF4. This catalytic alternative of the Ullmann reaction has proved to be sensitive to both electronic and steric factors of substrates.

Studies on sulfinatodehalogenation——ⅪⅩ.The reaction of perfluoroalkyl iodides and perfluoroalkane-sulfonyl bromides with conjugated dienes

The reaction of TbCl_3 with K[2,4-(CH_2)_2C_5H_5] at 0℃ in THF followed by crystalliza- tion at -90℃ led to a pale yellow hexagonal prismatic crystalline product [2,4-[CH_3)_2-η~5-C_5H_5]_(2-) Tb·1/2THF, which is highly sensitive to air and water and rapidly efflorescent at ambient temper- ature. The single Crystal X-ray diffraction data of the compound have been collected at low tem- perature (-60℃) and the crystal structure has been solved by heavy atom method. It belongs to triclinic system, space group Pl with lattice parameters a=8.477 (?),b=12.583 (?),c=12.858 (?), a=118.08°,β=91.38°,γ=108.75°,V=1120.36 (?)~ 3 and Z=2. Least-squares refinement converged to a final value R=0.043. The compound possesses an idealized G_(2h) symmetry、with three 2,4- dimethylpentadienyl ligands bound to the central terbium atom in a pentahapto mode (η~5). Each unit cell contains two molecules of[2,4-(CH_3)_2-η~5-C_5H_5]_3Tb and one molecule of solvent THF, of which the role in the lattice has been discussed in detail.

Studies on sulfinatodehalogenation ⅩⅩⅧ.The addition of polyfluoroalkyl iodides to olefins initiated by sodium disulfite

Polyfluoroalkyl iodides reacted with olefins in aqueous DMF solution of sodium disulfite under mild conditions to give the corresponding 1:1 adducts in good yields,providing a convenient polyfluoroalkylation method.This indicated that R_F radicals were formed in the reaction of polyfluoroalkyl iodides and sodium disulfite.A SET mechanism is proposed for the sulfinatodehalogenation reaction of sodium disulfite.