Dipolar Cycloaddition Reactions with Thiazolonylhydrazones: A New Route for the Synthesis of Several New Thienyl- and Furyl-Thiazolonylpyrrolopyrazole Derivatives of Expected Biological Activities

Several new pyrrolopyrazoles were synthesized via the reactions of each of 2-thiophenecarboxaldehyde thiazolonylhydrazone or 2-furaldehyde thiazolonylhydrazone with N -substituted maleimides followed by partial dehydogenation using bromobenzene and complete aromatization using nitrobenzene. Structures were established on the basis of elemental analyses and spectroscopic data studies.     

New Reactions with Cyanic Esters

The reactions of cyanic esters with acylating agents and the reactions of the resulting N-acyliminocarbonic ester halides are surveyed, and syntheses of heterocycles with cyanic esters and their reaction products are then reported.     

New Reactions of Halogenphosphoranes with Quinones

Abstract

It has not been known up to now that PCl₅ and p-benzoquinone can interact and form stable products. We have established that at the first stage of the reaction phosphorane (I) is formed which further undergoes different transformations depending upon the conditions.     

Parahydrogen Induced Polarization: A New Magnifying Glass for Examining Reactions with Hydrogen

Parahydrogen-included polarization (PHIP), its occurrence and mechanistic implications in homogeneous hydrogenation chemistry, and its appearance in the oxidative addition of H₂ to transition metal centers are described and analyzed. The PHIP phenomenon, which is characterized by unusual NMR absorptions and emissions in product spectra, arises when para-enriched H₂ is employed in hydrogenation of unsaturated organic substrates with a homogeneous metal catalyst or when para-enriched H₂ is added to a metal complex to form a metal dihydride. Examples of PHIP are found in ruthenium phosphine-catalyzed hydrogenations, catalysis by binuclear rhodium complexes, and in H₂ oxidative addition to Ir(I) complexes. The decay of polarization has been shown in the case of asymmetric hydrogenation catalyzed by Rh(chiraphos)⁺ to correlate well with the measured rate of reaction. For asymmetric hydrogenation of aprotic substrates using Noyori's Ru(BINAP)(OAc)₂ catalyst (1), PHIP is observed indicating a pairwise hydrogen transfer mechanism. Through the signal enhancement of PHIP, it has been possible to observe Rh hydride species never previously detected including binuclear complexes in the reaction of H₂ with RhCl(CO)(PR₃)₂ (R = Ph, Me) and in hydrogenation catalysis promoted by RhCl(PPh₃)₃. Also observed in the hydrogenation catalysis is the putative olefin dihydride catalytic intermediate.     

Reactions of early-late heterobimetallics with oxiranes: New examples for cooperative reactivity

In the reaction of oxiranes and cobalt-containing early-late heterobimetallic (ELHB) compounds isolated or prepared in situ, acyl-cobalt complexes, Y₃M^EOCHRCH₂C(O)Co(CO)₄ (1, M^E = Ti, Zr, Hf), were obtained. Some of the complexes 1 were isolated in form of their derivatives substituted on the cobalt atom with PPh₃. We have demonstrated that the ELHB compounds containing Group 4 metals and silyl-cobalttetracarbonyls are analogous concerning their reactivity against oxiranes. The studied heterobimetallic systems mediated the rearrangement of terminal oxiranes to ketones.     

Stereoselection at the Steady State: The Design of New Asymmetric Reactions

Not a new principle , but a shrewd analysis of stereoconvergent reactions is leading to new and highly efficient asymmetric reactions. A prochiral compound can be converted through a clever combination of competing reactions, one of which must be stereoselective, into a sole chiral product (shown above). The strategy is reviewed by using a radical cyclization reaction as an example.     

Pyridoxal: A New Alkylating Agent in Reactions with Phenols and Polyphenols

A possibility to use pyridoxal as an alkylating agent in the reactions of electrophilic mono-, di-, and trisubstitution in the aromatic core of various phenols and polyphenols was demonstrated for the first time. New types of hydroxyl-containing aromatic aldehydes containing vitamin B6 fragment were obtained, and the conditions for their synthesis were optimized.     

A New Approach to Inducing Silicon Tethered Ring-closing Metathesis Reactions

IntroductionGrubbs catalyst bis(tricyclohexylphosphine)benzylidene ruthenium( ) dichloride1 can be usedin a variety of ring- closing metathesis (RCM )reactions,cross metathesis(CM) reactions andring- opening metathesis polymerization(ROMP) [1— 4 ] .It remains metathetically active inthe presence of a variety of functional groups,suchas carbonyls,alcohols,and amides[1] .The use ofcatalyst1 in the synthesis has drawn more andmore attention[5— 13] . However,this catalyst is veryexpensive,an…     

Reactions of aldehyde with collagen: a DFT study

Structural Chemistry - The reaction mechanisms of several amino acids (Asn, Gln, Arg, His, and Lys) in the collagen with aldehyde were studied using density functional theory method. Based on the...     

Intersalation Reactions of Trisdiimine Metal Complexes with Montmorillonite Clay: A New Approach

Intersalation reactions of the complexes [Ni(L-L)(3)]SO(4) and [Ni(L-L)(3)]Cl(2) (L-L=1,10-phenanthroline (phen), 2,2'-bipyridyl (bpy)), with Na-montmorillonite carried out under different dynamic conditions such as ultrasonic irradiation, refluxing, autoclaving, and vigorous stirring showed that under ultrasonic irradiation, maximum adsorption of the metal complexes occurred within a period of 30 min. Metal complexes containing the phen ligand showed higher adsorption than those containing bpy. Maximum adsorption up to about three times the cation exchange capacity (CEC) of the clay was observed. Aggregated (basal spacing d(001) 12.5 ?) Na-montmorillonite, in treatment with a higher amount (>CEC) of metal complexes, formed monolayered (basal spacing d(001) 17.6 ?) species, while with predispersed clay, bilayered (basal spacing d(001)>28 ?) or pseudo-trilayer (basal spacing d(001)>32 ?) species were formed. The bilayered species were thermally stable up to 250 degrees C and above this temperature monolayered species were formed. The thermal stability of the intersalated species was higher than that of the intercalated ones. X-ray diffraction, UV-visible, IR-spectroscopy, thermal analyses, and surface area measurements were used for characterization of the products. Copyright 2001 Academic Press.     

Reactions of organic anions—L : Reactions of phenylacetonitrile derivatives with aromatic nitrocompounds in basic media

Reaction of phenylalkanenitriles and diphenylacetonitrile with aromatic nitro compounds were studied using various base-solvent systems. Four independent types of reaction: substitution of halogen, substitution of nitro group, substitution of hydride anion and electron transfer were observed. Relationship—reaction pathway—conditions have been discussed.     

过渡金属团簇M+2(M=Fe、Co、Ni)与CO的化学反应

利用离子讲质谱计和激光溅射技术相结合,研究了Fe2＋、CO2＋、Ni2＋与CO气体的吸附反应,比较了它们的反应活性,给出了化学反应的速率常数及随反应气体压强的变化关系,并从理论上模拟了化学反应过程,测量结果与已有的实验值符合较好．     

Reactions of lanthanide acetylacetonates with triethylaluminum

The reactions of lanthanide acetylacetonates Ln(acac)₃ · H₂O (Ln = Nd, Tb, Ho, Lu) with Et₃Al in toluene were studied by spectral methods (photoluminescence; taumetry; NMR, IR, and UV-vis spectroscopy) using GLC, volumetry, and chemical analysis.     

Synthesis and Reactions of New Dithiolopyrroles

The title compounds were prepared starting from pyrrolinone 4 . Nucleophilic‐displacement and ring‐closure reactions yielded the dithiolopyrrole 5a , which formed salts with electrophiles ( 7, 8 ) as well as with bases. The crystal structure of 5a was determined. Oxidation of the dithioles 5a and 6a led to S(2)‐oxides ( 10a, 11a ) and the corresponding S(2)‐dioxides ( 10b, 11b ) depending on reaction conditions. The thiosulfinate 10a was converted by a ring‐opening/ring‐closure reaction sequence to the bicyclic sulfinamide 12 . The oxidative addition reactions of [Pt(η²‐C₂H₄) (PPh₃)₂] ( 14 ) with the disulfides 5a and 13 led to the dithiolatoplatinum(II) complexes 15 and 16 , respectively. Complex 16 was characterized structurally. The sulfenato‐thiolato complex 17 was synthesized via reaction of 14 with the thiosulfinate 10a . The thiosulfonato Pt^II complex 18 was prepared by an oxidative insertion of Pt⁰ into the C? S bond of the corresponding thiosulfonate 10b . Furthermore, complex 18 was characterized by single‐crystal X‐ray‐diffraction studies.     

镍催化芳基-芳基交叉偶联反应的配体研究新进展

联芳基结构在天然产物、药物以及各种光电材料中广泛存在,自20世纪70年代以来,各种过渡金属催化的芳基-芳基偶联手段得到普遍应用,配体、底物、辅助手段等的研究也快速发展.从配体类型的角度综述了镍催化的芳基-芳基交叉偶联反应.     

New Reactions with Thioaldehydes and Thienium Cations

Abstract

i) When generated under FVT conditions α-imino-thioaldehydes undergo a cyclization to dihydro-1,3-thiazoles. ii) Thienium cations, generated during a Pummerer reaction, can be trapped with dienes.     

Reactions with Hydrazonoyl Halides 341: Synthesis of Some New 2,3-Dihydro-1,3,4-thiadiazoles

Hydrazonoyl halides 4a–h have been caused to react with each of alkyl carbodithioates (3, 13–17)a,b in the presence of triethylamine to give 2,3-dihydro-1,3,4-thiadiazoles in good yields. Structures of the new compounds were elucidated on the basis of elemental analyses, spectral data, and alternative methods of synthesis whenever possible.