Electronic properties of furyl substituents at phosphorus and their influence on 31P NMR chemical shifts

The electronic properties of 2-furyl and 3-furyl substituents attached to phosphanes and phosphonium salts were studied by means of IR spectroscopy and experimental and computational (31)P NMR spectroscopy. The heteroaromatic systems proved to be electron withdrawing with respect to phenyl substituents. However, phosphorus atoms with attached furyl substituents are strongly shielded in NMR. The reason for this phenomenon was studied by solid state (31)P MAS NMR experiments. The chemical shift tensor was extracted, and the orientation within the molecules was determined. The tensor component sigma(33), which is effected the most by furyl systems, is oriented perpendicular to the P-C bonds of the substituents. P-furyl bonds are shorter than P-phenyl bonds. We assume therefore a lower ground-state energy of the molecules, because of the electron withdrawing properties of the 2-furyl systems. The sigma(para) component of the (31)P NMR magnetic shielding is therefore smaller, which results in an overall increase of the magnetic shielding.     

Synthesis of phenyl furyl sulfides and phenyl furyl ethers by nucleophilic substitution of nitrofurans

Phenyl furyl sulfides ( 3a‐j ) and phenyl furyl ethers ( 3k‐n ), which are useful in synthesizing furocondensed 3‐ring compounds, can be synthesized by nucleophilic substitution of nitrofurans having electron withdrawal groups. In our experiments using 5‐nitrofurans having electron withdrawal groups ( 2a‐i ), nucleophilic substitution readily occurred with the benzenethiolate anion of thiosalicylic acid ( 1a ), the benzenethiolate anion of thiosalicylate ester ( 1b ), and the phenylate anions of salicylate esters ( 1c‐d ) to yield phenyl furyl sulfides ( 3a‐j ) and phenyl furyl ethers ( 3k‐n ).     

Cyclizations of some furyl acid chlorides

Intramolecular Friedel-Crafts acylation of the furan ring has been accomplished in good yields with stannic chloride for both furyl isomers of butyryl acid chloride. The propionyl chloride isomers, however, failed to produce reasonable quantities of the cyclic ketone.     

Halogenation of thenyl and furyl cobaloximes

The reactions of thenyl and furyl cobaloximes with halogens (bromine and chlorine) in acetic acid and chloroform indicate that, CoC bond cleavage occurs in 2-thenyl and 2-furyl case whereas the ring substitution is faster than CoC band cleavage in 3-thenyl and 3-furyl cobaloximes.     

Thiapyrylium and pyrylium salts with furyl substituents

The possibility of obtaining pyrylium and thipyrylium salts that contain acidophobic furyl substituents by the action of protic acids on the corresponding 1,5-diketones in acetic acid or methanol, depending on the position of the furan rings relative to the carbonyl groups, was established.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1604–1607, December, 1981.     

Short and efficient synthesis of chiral furyl carbinols from carbohydrates

[reaction: see text] Common sugar derivatives can be transformed in a few steps into chiral-substituted furyl carbinols. The mildness of the reaction conditions and the good yields obtained make this procedure an interesting alternative to the conventional processes.     

Mass-spectrometric thermal analysis of polymers based on furyl alcohol

Mass-spectrometric thermal analysis of samples of furan polymers obtained by heating furyl alcohol in a closed volume at 200 °C, 250 °C and 300 °C permitted determination of the qualitative composition of the gas products evolved from the polymers upon non-isothermal temperature increase from 20 to 1200 °C. The degree of unsaturation of the samples was evaluated quantitatively. The main features of the formation, degradation, structurization and carbonization of furan polymers were considered.     

Syntheses of furo[3,4-c]coumarins and related furyl coumarin derivatives via intramolecular Wittig reactions

A new and general strategy for highly functional furo[3,4-c]coumarins and related furyl coumarin derivatives has been developed, which is based on an extraordinarily facile intramolecular Wittig reaction, starting from α,β-unsaturated ketones, tributylphosphine, and acyl chlorides. The phosphorus ylides were proposed to be the key intermediates for constructing the crucial furan ring, leading to a wide variety of substituted furyl coumarins in one step.     

呋喃和苯多烯醛分子中的共轭效应和共轭基干

呋喃和苯多烯醛系列的CNDO/2和微扰分子轨道法的计算表明, 共轭效应与共轭基干是两个不同的概念, 共轭效应包括了共轭基团之间的作用对分子性能全面的影响, 而共轭基干仅仅反映了共轭基团间的作用对前沿分子轨道的影响。这意味着, 相互之间有共轭作用的基团不一定属于同一个基干, 属于同一个共轭基干的基团之间, 必定有共轭作用。共轭基干更确切的反映了共轭基团间的作用对分子结构的依赖。     

Synthesis of alkyl and alkenyl furyl sulfoxides and their behavior in the pummerer reaction

Oxidation of alkyl(alkenyl) furyl sulfides by hydrogen peroxide in glacial acetic acid affords alkyl(alkenyl) furyl sulfoxides, which react with acetic acid, acetic anhydride, and a mixture of acetic and trifluoroacetic anhydrides to give -acyloxy-substituted and unsaturated sulfides as products, while for allyl 2-(5-methylfuryl) sulfoxide a thienofuran compound is obtained.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1601–1604, December, 1987.     

Derivatives of furyl(diethoxyphosphoryl)acetic aldehyde in Wittig reaction

Reactions of furyl(diethoxyphosphoryl)acetic aldehyde containing ester or cyano group in the furan ring with ethoxycarbonylmethylenetriphenylphosphorane has been shown to afford alkyl E-4-(furyl)-4-(diethoxyphosphoryl)but-3(2)-enoates. When treated with potassium tert-butoxide the mixture of alkyl E-4-(3-ethoxycarbonylfur-2-yl)-4-(diethoxyphosphoryl)but-2-enoate and -but-3-enoate gives a potassium salt of CHacid. Its acidifying results in a mixture of starting compounds with a larger amount of -but-3-enoate. Under analogous conditions the mixture of alkyl E-4-(2-ethoxycarbonylfur-3-yl)-4-(diethoxyphosphoryl)but-2-enoate and -but-3-enoate undergoes cyclization to a phosphorylated derivative of alkyl 7-hydroxybenzofuran-6-carboxylate. The cyclization of the mixture of alkyl E-4-(4-ethoxycarbonylfur-3-yl)-4-(diethoxyphosphoryl)but-2-enoate and -but-3-enoate gives analogous derivative of isobenzofuran.     

Divergent reaction pathways of a cationic intermediate: rearrangement and cyclization of 2-substituted furyl and benzofuryl enones catalyzed by iridium(III)

In contrast to 2-substituted pyrrole enones, furyl and benzofuryl enones do not undergo the Nazarov electrocyclization. Instead, these furyl and benzofuryl enones exhibit unusual rearrangement sequences in the presence of catalytic amounts of [IrBr(CO)(DIM)((R)-(+)-BINAP)](SbF(6))(2) (1; DIM = diethylisopropylidene malonate) and AgSbF(6) (1:1). A 1,2-H shift followed by intramolecular Friedel-Crafts alkylation leads to synthetically valuable cyclohexanones with furanylic quaternary centers. The electrophilicity of 1 is essential for this rearrangement.     

Photo switchable pendant furyl and thienyl fulgimides containing polypyrroles

We report the new pendant furyl and thienyl fulgimides photochromic switch bearing polypyrroles. The functionalized pyrrole monomers synthesized and structures are ascertained by NMR and mass spectral techniques. The yield of fulgides and fulgimides are improved by using trifluoroacetic anhydride (TFA) as a dehydrating agent. The photo-switching properties of fulgimides monomers are explained by electronic structures of HOMO–LUMO of the monomers using Gaussian 03 packages. The electro-active polymer films deposited on indium tin oxide (ITO) electrodes are characterized by cyclic voltammetry and atomic force microscopy (AFM). The electrochemically formed thin films undergoes photo-switching between open and closed state of fulgimides moiety. The photo-switching properties of the polymer films have been confirmed by UV/vis spectroscopy. Though the films are photochemically stable, their mechanical stability with respect to adhesion to electrode is found to be sensitive to the solvent and electrode material.     

Synthesis and kinetic resolution of furyl substituted secondary carbinols by porcine pancreatic lipase under solvent free conditions

Chiral furyl substituted carbinols were prepared from the related carbonyl compounds and their enzymatic kinetic resolution was studied by using porcine pancreatic lipase (PPL) in transesterification reaction under solvent free condition. This study revealed that carbinols having one less bulky group on the chiral center are good substrates for PPL and the resolution proceeds with higher ee,s and less reaction time.     

Cu(OTf)2 Catalyzed Synthesis of Bis(5‐methyl‐2‐furyl)methanes by Condensation of 2‐Methylfuran with Carbonyl Compounds under Solvent Free Conditions

A facile and efficient one‐pot three‐component synthesis of bis(5‐methyl‐2‐furyl)methanes has been achieved via the reaction of 2‐methylfuran with a series of aliphatic and aromatic aldehydes and aliphatic ketones in presence of copper(II) triflate under solvent free conditions. The bis(5‐methyl‐2‐furyl)methanes were obtained in 34% –72% yields and the catalyst was recycled up to four successive cycles without much loss in catalytic activity.     

Metal-catalyzed asymmetric oxidations mediated by optically pure furyl hydroperoxides

Metal-catalyzed asymmetric oxidations which rely on the use of commercially available t-butyl (TBHP) or cumyl hydroperoxides (CHP) and enantiopure ligands represent the majority of protocols reported to obtain enantiomerically enriched valuable compounds such as epoxides, sulfoxides, diols, etc. Herein, we review our recent results on the complementary and less studied oxidative approach based on the use of optically pure alkyl hydroperoxides as oxygen and chirality source. The synthetic sequence to enantiopure furyl hydroperoxides, easily accessible from ketones of the chiral pool is firstly described. Examples of metal-catalyzed asymmetric oxidations using these compounds for the production of enantiomerically enriched sulfoxides and epoxy alcohols are shown. The entire protocol is made more advantageous by recovering the optically pure alcohols during the purification procedure and recycling them for the one-step synthesis of the hydroperoxides.     

An efficient synthesis of furyl sulfonamides from the reaction of furan with in situ generated N-tosyl imines

Treatment of an aldehyde and furan with N-sulfinyl-p-toluenesulfonamide/zinc chloride leads to the formation of furyl sulfonamides via an in situ generated N-tosyl imine intermediate. In one case, a novel 4-tosylamino-5,6-dihydro-4H-3-oxa-benz[e]azulene was obtained by intramolecular aromatic substitution of the activated imine at the 3-position of the furan ring.     

The fast atom bombardment mass spectra of furyl and thienyl silanes and germanes in comparison with their electron impact mass spectra

The interaction of the π electron system of furyl and thienyl substituents with the silicon (or germanium) atom is less significant in fragmentation under fast atom bombardment than under electron impact. Under fast atom bombardment the primary fragmentation of the title compounds is determined by steric influence of the heteroaromatic substituents.     

Tuning of electronic structures of poly(p-phenylenevinylene) analogues of phenyl, thienyl, furyl, and pyrrolyl by double-bond linkages of group 14 and 15 elements

We investigated electronic structures of four sets of monomers and polymers comprising of phenyl rings and five-membered hetero(aromatic) moieties connected with double-bond -X=X- linkages (X = CH, SiH, GeH, N, P, As) by density functional theory, time-dependent density functional theory, and periodic boundary condition calculations with B3LYP functional. Electronic structures of poly(p-phenylenevinylene) (PPV) analogues are primarily dominated by central double-bond moieties. The introduction of ethylene homologues with group 14 and 15 elements was demonstrated to be a promising approach to modify electronic structures of conjugated oligomers and polymers. Excitation energies of monomers with double-bond linkages were reduced by around 13-50% with respect to corresponding dimers of phenyl, thienyl, furyl, and pyrrolyl rings. Similarly, band gaps of poly(p-phenylene) and polythiophene were decreased by 0.3-0.9 eV upon the insertion of double-bond linkages. Furthermore, excitation energies of monomers presented decreasing trends when descending through groups 14 and 15. For group 14 ethylene homologues, the decreasing trend in the lowest excitation energies was rationalized by a progressively favoring of pi-sigma* interactions as descending X = CH, SiH, and GeH. Increasing p contents of central bonds along X = N, P, and As accounted for geometry features and the lowest excitation energies of group 15 species. A decrease in the extent of electronic communications between aromatic rings and -X=X- linkages within higher congeners was also revealed.     

Preparation and characterization of a new meso-substituted tetrapyrrole macrocyclc: Meso-tetra[2-(3-carboxyethyl)furyl]porphine, [TFP]

The preparation of meso-substituted tetrafuryl-porphines is described. These new compounds are very soluble either in organic solvent or in water depending upon the furyl groups substitution. Their spectroscopic absorption, nmr characteristics, and some of their electrochemical properties are reported.