Solid-phase Synthesis of a Novel Kind of Hydroxylated Heterocyclic Ketene Aminals

An efficient solid-phase synthesis method for novel heterocyclic ketene aminals containing a hydroxyl group has been developed. The loading of the substrate on the resin through the hydroxyl group and the protection of the amine by the Schiff base were the key steps in the synthesis.     

New Synthesis of α-Bromo-α,β-Unsaturated Esters

A synthesis of α-bromo-α,β-unsaturated esters 2 from tert-butyl α-(trimethylsilyl)-α-bromoacetate (1) and carbonyl compounds is described.     

Synthesis of α,β-Unsaturated Nitriles by Reaction of Haloacetonitrile with Carbonyl Compounds Mediated by Tri-n-butylstibine

α,β-Unsaturated nitriles were synthesized by the reaction of haloacetonitriles with carbonyl compounds mediated by tri-n-butylstibine in excellent yields.     

A Novel One-Pot Synthesis of Fluorinated α,β-Unsaturated Esters

The reaction of pentafluorophenylmethylene-triphenylarsorane or p-chloro-tetrafluorophenylmethyl-enetriphenylarsorane, generated in situ from methylene-triphenylarsorane and hexafluorobenzene or chloropenta-fluorobenzene, with bromoacetates giving excellent yields of 3-pentafluorophenyl or 3-p-chloro-tetrafluoro-phenyl α, β-unsaturated esters with high steroselectivity is described.     

Low-valent Titanium Induced Reductive Coupling Reaction of Aryl Sulfonyl Chlorides with α,β-Unsaturated Esters

Thereductivecouplingreactionofthecarbonylcompoundsbylow-valenttiboiumSPecieshasbeenstUdiedindepthandhaswidelybeenusedinorganicsynthesis"'.However,theintermolecu1arreductivecouplingreactionoftWocompoundscontainingdifferentfunctionalgroupsinducedbylow-valenttitaniumhasnot'beenreported.Recently,wehavereportedthelow-valenttitaluminducedintermolecularreductivecouplingreactionsofcarboxylicderivativeswithketones',andcarboxylicderivativeswithnitrocompounds'.Wenowdescribetliereactionofarylsulfonylchl…     

Coupling Reaction of Isothiocyanates or Isocyanates with α, β-Unsaturated Esters Mediated by SmI2

α,β-unsaturated ester coupled with isocyanates or isothiocyanates to give the corresponding thioamides or amides in good yields by SmI₂ in the presence of HMPA and t-BuOH in THF at-78°C within a few min.     

Chemoselective Catalytic Hydrogenation of α,β-Unsaturated Ketones and α,β-Unsaturated Carboxylic Esters

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Synthesis of α,β-Unsaturated Nitriles from the Iodine Catalyzed Reaction of Chloroacetonitrile with Aldehydes Promoted by Tri-n-Butylarsine and Magnesium

α,β-Unsaturated nitriles were synthesized from the iodine catalyzed reaction of chloro-acetonitrile with aldehydes promoted by tri-n-butylarsine and magnesium.     

α-Oxo Ketene Dithioacetals Chemistry-A Facile Route to the Synthesis of Fused Heterocyclic Compounds

Q-Oxo ketene dithioacetals and related compounds are versatile synthons in organicsynthesis'-'. The substitution reaction of or-oxo ketene dimethylthio acetals with diamineis one of the impel'tant applications for the synthesis of corresponding a-oxo ketenecyclic N, N-acetals. Junjappa and co-workers described this reaction ill a review'.However, since some kinds of ketene dimethylthio acetals are not easy to prepare, themethod melltioned above is limited. Zhu and co-workers had successfully…     

Intelligence Way from Eco-friendly Synthesis Strategy of New Heterocyclic Pyrazolic Carboxylic α-Amino Esters

The α-amino acid derivatives constitute a class of compounds of particular medicinal and synthetic attention and considerable interest has been devoted to their synthesis in recent years. In the present work, we develop the computational study of the synthesis reaction of new pyrazolyl α-amino esters derivatives using the Gaussian 09 based on the DFT/B3LYP density functional theory method, with the base 6-31G(d, p) to ensure the possibility of carrying out these reactions within the laboratory of synthesis. Indeed, this research has encouraged us to establish an economical synthesis strategy of these products in overall yields of 73.5% to 87% to have access to new active biomolecule through the O-alkylation reaction between methyl α-azidoglycinate N-benzoylated and primary pyrazole alcohols[(3,5-dimethyl-1H-pyrazol-1-yl)methanol, (1H-pyrazol-1-yl)methanol and (3-ethoxy-5-methyl-1H-pyrazol-1-yl)methanol] under different operating conditions. The structure of the prepared heterocyclic systems was characterized by conventional spectroscopic techniques, like ¹H NMR, ¹³C NMR, and MS. The results revealed that the experimental study is in good correlation with the computational one.     

Reaction of Trialkyl Phosphites with α,β-Unsaturated Carbonyl Compounds

Abstract

Reaction of trialkyl phosphites 1 with α,β-unsaturated oxo-compounds 2 gives oxaphospholenes 3 or/and two types of Arbuzov products, γ-keto-phosphonates 4 and alkyl-enol-ethers 5.     

Studies on the Silylation Reaction of α,β-Epoxy Esters Synthesized by Darzen's Condensation Reaction

Me₃SiCl/Mg in HMPA was used for silylation of α,β-epoxy esters resulting in the corresponding β-silylated esters in a one pot reaction with reasonable yields.     

A Substrate-Driven Approach to Determine Reactivities of α,β-Unsaturated Carboxylic Esters Towards Asymmetric Bioreduction

The degree of C?C bond activation in the asymmetric bioreduction of α,β-unsaturated carboxylic esters by ene-reductases was studied, and general recommendations to render these "borderline-substrates" more reactive towards enzymatic reduction are proposed. The concept of "supported substrate activation" was developed. In general, an additional α-halogenated substituent proved to be beneficial for enzymatic activity, whereas β-alkyl or β-aryl substituents were detrimental for the reactivity of nonhalogenated substrates, and α-cyano groups showed little effect. The alcohol moiety of the ester functionality was found to have a strong influence on the reaction rate. Overall, activities were determined by both steric and electronic effects.     

The Reaction of N-Phenyliminoketenylidenetriphenyl-phosphorane with α,β-Unsaturated Carbonyl Compounds. Synthesis of New Pyran Derivatives

Abstract

The reaction of N-phenyliminoketenylidenetriphenylphosphorane [a] (1), with 2-benzylidene-1, 3-indandione (2), 1,2-diphenyl-3,4-pyrazolidenedione (3)and/or 5-benzylidene barbituric acid (4) has been investigated. When ylide 1 was allowed to react with compounds 2, 3 or 4 in THF at ambient temp. the corresponding new pyrano-phosphoranylidenes 5, 6 or 7 were obtained. The elemental microanalyses, IR, ¹H NMR, ³¹P NMR and MS data agree with the structure of the cyclic iminophosphoranes by [4+2]-cycloaddition and exclude 4-membered ring structure by [2+2]-cycloaddition. When the Wittig reaction was carried on the pyrano-phosphoranes 5, 6 or 7 using p-nitrobenzaldehyde, the exocyclic olefins together with triphenylphosphine oxide were isolated.     

Highly Enantioselective Iridium-Catalyzed Hydrogenation of α,β-Unsaturated Esters

α,β-Unsaturated esters have been employed as substrates in iridium-catalyzed asymmetric hydrogenation. Full conversions and good to excellent enantioselectivities (up to 99?%?ee) were obtained for a broad range of substrates with both aromatic- and aliphatic substituents on the prochiral carbon. The hydrogenated products are highly useful as building blocks in the synthesis of a variety of natural products and pharmaceuticals.     

The Reaction of 1-Aryl-2-(4-nitrophenylsulfonyl)ethanones with α,β-Unsaturated Esters

1-Aryl-2-(4-nitrophenylsulfonyl)ethanones (1) reacted with one equiv. of α,β-unsaturated esters at 60°C to afford the tandem addition-rearrangement products (3), while at 75°C 1a reacted with two equiv. of methyl acrylate and gave an unexpected addition-rearrangement-addition-annulation product which is dimethyl 4-hydroxyl-1-(4-nitrophenyl)-4-phenyl-1,3-cyclohexyldicarboxylate (4). A mechanism is suggested.     

Stereoselective Cycloaddition of N-Acyliminium Ions with α,β-Unsaturated Ketones and Esters

The [4+2] reactions of N‐acyliminium ions, produced from 2‐aryl‐3‐hydroxy‐2,3‐dihydroisoindol‐1‐ones or 5‐hydroxy‐1‐phenyl‐2,5‐dihydro/2,3,4,5‐tetrahydropyrrol‐2‐ones in the presence of BF₃OEt₂, with α,β‐unsaturated ketones or esters were examined, and the dependence of these reactions on the substituents at double bonds was clarified. For β‐aryl substituted α,β‐unsaturated ketones and esters such as 4‐aryl‐3‐buten‐2‐ones, chalcones and methyl cinnamate, the [4+2] reactions could proceed smoothly at room temperature to afford 6‐acyl‐5,6,6a,11‐tetrahydroisoindolo[2,1‐a]quinolin‐11‐ones and 4‐acyl‐1,3a,4,5‐tetrahydropyrrolo[1,2‐a]quinolin‐ 1‐ones or 4‐acyl‐1,2,3,3a,4,5‐hexahydropyrrolo[1,2‐a]quinolin‐1‐ones in moderate to high yields; while for simple α,β‐unsaturated ketones and esters such as methyl crotonate and ethyl 3‐methylbut‐2‐enoate, except mesityloxide, the [4+2] reactions were difficult to proceed. The cycloaddition reactions were highly stereoselective, and only one stereoisomer was produced in each reaction.     

Organocatalytic Enantioselective Diels–Alder Reaction of 2-Trifluoroacetamido-1,3-dienes with α,β-Unsaturated Ketones

We report herein the first examples of chiral phosphoric acid-catalyzed enantioselective Diels–Alder reactions between 2-trifluoroacetamido-1,3-dienes 1 and α,β-unsaturated carbonyl compounds 2 . Polysubstituted 1-acetamido cyclohexenes 3 were formed in high yields with excellent diastereo- and enantioselectivities. The reaction proceeds through a stepwise process as shown by deuterium labelling experiments. A catalytic enantioselective three-component reaction of 1 , 2 and ortho-hydroxybenzhydryl alcohols 4 was subsequently developed furnishing the densely functionalized hexahydroxanthenes 5 in a highly stereoselective manner. This multicomponent reaction generates four chemical bonds with concurrent creation of five contiguous stereocenters.