Reactions of Electron-Rich Olefins

Olefins are normally preferentially attacked by electrophiles. This trend is strengthened in enol ethers and enamines, and is particularly pronounced in tetramethoxyethylene and in tetraaminoethylenes. These electron-rich olefins are accordingly also excellent reducing agents. In their reactivity, therefore, they behave as counterparts of tetracyanoethylene. This compound shares with the electron-rich olefins a strong tendency to undergo cycloadditions, the electron-rich olefins adding particularly readily to electrophiles.     

Reactions of Electron-Rich Olefins with Proton-Active Compounds

Abstract: From the reaction of electron-rich olefins, bis(1,3-dimethylbenzimidazolidine-2-ylidene), I, or bis(3-methylbenzothiazolidine-2-ylidene), II with proton active compounds, such as dimethyl phosphite, diethyl phosphite, acetonitrile and benzaldehyde were obtained 2-substituted benzimidazole or benzothiazole derivatives. The compounds synthesized were identified by ¹H, ¹³ C, ³¹P-NMR, mass, FT-IR spectroscopic techniques and micro analysis.     

亲电性对醌二甲烷与富电子烯烃的电荷转移聚合

概述了亲电性对醌二甲烷与富电子烯烃电荷转移聚合的最新进展，着重介绍聚合的一般特征、引发机理、链增长机理，以及单体结构、溶剂对聚合反应的影响。     

Allylic Functionalization of Unactivated Olefins with Grignard Reagents

New advances in the functionalization of unactivated olefins with carbon nucleophiles have provided more efficient and practical approaches to convert inexpensive starting materials into valuable products. Recent examples have been reported with stabilized carbon nucleophiles, tethered carbon nucleophiles, diazoesters, and trifluoromethane donors. A general method for functionalizing olefins with aromatic, aliphatic, and vinyl Grignard reagents was developed. In a one‐pot process, olefins are oxidized by a commercially available reagent to allylic electrophiles, which undergo selective copper‐catalyzed allylic alkylation with Grignard reagents. Products are formed in high yield and with high regioselectivity. This was utilized to synthesize a series of skipped dienes, a class of compounds that are prevalent in natural products and are difficult to synthesize by known allylic alkylation methods.     

Selective Reactions with Organoaluminum Compounds

With the aid of selected examples an overview is given of the development trends in highly discriminative reactions using organoaluminum compounds. (1) Isomerization of substituted oxiranes into allyl alcohols has been effected both stereo- and regioselectively by means of a new organoaluminum reagent, diethylaluminum 2,2,6,6-tetramethylpiperidide (DATMP); this reaction which provides a new route for the regiospecific transformation of allyl alcohols into 1,3-dienes. (2) A novel nonenzymic heterolysis of allylic phosphates of terpenoids has been effected by organoaluminum compounds and has enabled development of a new method for the selective synthesis of cyclic terpenes. (3) The reductive condensation of α-haloketones with carbonyl compounds in the presence of diethylaluminum chloride and zinc affords β-hydroxy-carbonyl derivatives in good yields with exclusion of undesired self-condensations products.     

Coupling between Two NO Radicals Linked through Electron-Rich Rings

Design and synthesis of organic molecules in very high-spin ground states are currentsubjects of great importance'-#. A key to the rational design of these molectlles is theability' to control spin-spin coupling of unpaired electrons. One strategy being currentl}'pursued> is that a high-spin molecule can be divided into two components; the spillcontaining fragment (SC) and the ferromagnetic coupling unit (FC). The SC is simpl}'any structure that provides the unpaired electrons, and the FC i…     

Ground State Spins of Bicarbcnes and Binitrenes,Coupled through Electron-Rich Rings

Therationaldesignandsynthesisofmagneticorganicmolecularmaterialshasreceivedmuchattentioninthepastfewyears'-'.Onestrategybeingcurrentlypursued'isshownschematicallyinFigurela.Ahigh-spinmoleculecanbedividedintotwocomponentsfthespin-containingfragment(SC)andtheferromagneticcouplingunit(FC).TheSCissimplyanystructurethatprovidestheunpairedelectrons,andtheFCisageneralstructuralunitthatferromagneticallycouplesanytwoormoreSCs.Ashasbeenstressedpreviously',thekeyelementinthedesignofneworganicmagneti…     

Reactions of Aromatic Nitro Compounds with Bases

Aromatic nitro compounds can react in many ways with bases. The reaction path followed depends mainly on the degree of nitration (with a sharp jump from mononitro to di- and trinitro compounds) and the base used. Redox reactions or nucleophilic aromatic substitutions predominate with mononitro compounds, whereas Meisenheimer additions together with nucleophilic aromatic substitutions are preferred by dinitro and trinitro compounds; deprotonations are less common. The bromine in nitrobromobenzenes can be replaced by metal at low temperatures. Very weak bases generally give electron donor-acceptor complexes.     

Reactions of Enaminones with Diazocarbonyl Compounds

The [Cu(acac)₂]‐catalyzed reactions of several tertiary enaminones with three diazocarbonyl compounds, i.e., dimethyl diazomalonate, ethyl diazoacetoacetate, and ethyl diazoacetate, yielded amino‐ and additionally carbonyl‐substituted dihydrofurans, together with further furan derivatives. Due to the conjugation of α‐carbonyl/α‐Ph groups, reactions proceeded only via 1,5‐electrocyclization of corresponding keto‐ylides. On the other hand, in the absence of any α‐substituent, tertiary enaminone and ethyl diazoacetate, reacted via an accompanying mechanism by a push‐pull cyclopropane intermediate, to yield a 2,4‐dicarbonyl‐substituted furan in one step with moderate yield.     

Substitution effects on the catalytic activity of Mn(III)-porphyrins in epoxidation of alkenes with iodosylbenzene: A comparison between the electron-rich and electron-deficient porphyrins

Oxidation of different olefins with iodosylbenzene in the presence of Mn(III) complexes of meso-tetra(para-tolyl)porphyrin, meso-tetra(ortho-tolyl)porphyrin, meso-tetra(thien-2-yl)porphyrin and β-hexaboromo-meso-tetra(thien-2-yl)porphyrin as catalyst has been studied. Oxidation of cis- and trans-stilbene in a competitive reaction strongly suggests the involvement of a high valent (porphyrin)MnO as the active oxidant intermediate, in the case of each catalyst. Clear observation of the band relevant to a (porphyrin)Mn(IV)O species in the presence of excess amounts of styrene shows the stability of this moiety towards reaction with olefins. Although, the stability of metalloporphyrins towards oxidative degradation decreases in the order MnT(o-tolyl)P(OAc) > MnT(thien-2-yl)PBr₆(OAc) > MnT(p-tolyl)P(OAc) ? MnT(thien-2-yl)P(OAc), a complex pattern of catalytic activity and product (epoxide) selectivity has been found for the Mn-porphyrins in oxidation of various alkenes.     

Reactions of Selenobenzophenones with Olefins

Reactions of selenobenzophenones with methyl propiolate afforded two types of cycloadducts regioselectively. The reaction with tetracyanoethylene gave selenophene derivatives. Mechanisms of these reactions were discussed.     

Opportune gem‐Silylborylation of Carbonyl Compounds: A Modular and Stereocontrolled Entry to Tetrasubstituted Olefins

An easy access to highly versatile gem‐silylboronate synthons is achieved by means of a new olefination reagent, HC(Bpin)₂(SiMe₃). Subsequent silicon or boron‐based selective functionalization allows for the modular and stereocontrolled synthesis of all‐carbon tetrasubstituted alkenes. A particular attraction of this approach is the iododesilylation reaction, which becomes a pivotal tool for C?Si functionalization.     

C-Phosphorylation of Compounds with the Electron-Rich Double Carbon-Nitrogen Bond

Abstract

C-phosphorylation of N,N-dimethylhydrazones and N,N-dimethyl-N′-arylamidines by phosphorus tribromide was first accomplished. It directs to the formation of novel types of functional P(III) derivatives (1–3)     

FeCl3‐Catalyzed Addition of 1,3‐Dicarbonyl Compounds to Aromatic Olefins

A direct, intermolecular addition of 1,3‐dicarbonyl compounds to styrenes in the presence of FeCl₃ as an inexpensive and disposable catalyst has been developed for the straightforward and practical synthesis of arylated diketones and ketoesters. The reactions proceed under mild conditions for most substrates (50–80 °C), and no strong acid or base is required. The synthetic value of the method is demonstrated by 15 examples, including the synthesis of the current pharmaceutical drug warfarin in one step and 42 % yield from commercially available substrates.     

Highly diastereoselective synthesis of new chromenylaminoanthraquinones through a one-pot, three-component hetero Diels–Alder reaction

A new, efficient, and diastereoselective one-pot synthesis of cis-fused pyrano and furano chromenylaminoanthraquinones through hetero Diels–Alder reaction of 1-aminoanthraquinone and salicylaldehydes with electron-rich alkenes such as 3,4-dihydro-2H-pyran, 2,3-dihydrofuran, and ethyl vinyl ether under mild conditions is reported.