Alkyl Propiolates Research Articles

Acetylides from Alkyl Propiolates as Building Blocks for C3 Homologation

Alkyl propiolates are reagents with a versatile reactivity profile that entirely remains in the C(3)-homologated product for further elaboration. To be effective, this C(3) homologation requires suitable methods for the generation of the acetylide anion that are compatible with both the conjugated ester and the electrophilic partner. Recent advances include catalytic procedures for the in situ generation of these acetylides in the presence of suitable electrophiles. Whereas the organometallic methods have brought stereoselectivity to these reactions, the organocatalytic methods laid the ground for new efficient domino processes that generate complexity.

ChemInform Abstract: Novel Multicomponent Reactions of Primary Amines and Alkyl Propiolates with Alloxan Derivatives in Water.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Three-component process for the synthesis of some pyrrole derivatives under microwave irradiation

We report a short and efficient 3-component reaction for synthesis of a series of [1,2-b]pyrrole derivatives from ninhydrin, alkyl propiolates, and simple primary amines under solvent free and microwave irradiation. This method provides a new route to produce pyrrole derivatives in good to excellent yields.

Ambiphilic allenes: synthesis and reactivity

Ambiphilic allenes are generated by an organocatalyzed domino reaction of alkyl propiolates and aromatic 1,2-diketones; in the absence of any external chemical agent, these allenes perform a thermally-driven dimerization reaction to generate the corresponding fully-substituted cyclobutanes in a regio- and highly stereoselective manner.

ChemInform Abstract: Synthesis of Polyfunctionalized Alkenes and α,β‐Unsaturated γ‐Lactams from the Reaction of Alkyl Propiolates and CH‐Acids such as Diethyl Acetamidomalonate and Ethyl Acetamidocyanoacetate in the Presence of Triphenylphosphine.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: One‐Pot Synthesis of Functionalized Thioureas by Reaction of Benzoyl Isothiocyanates, Secondary Amines, and Alkyl Propiolates.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Synthesis of Alkyl 2-[2-oxopyridin-1(2H)-yl]acrylates by Nucleophilic Addition of Alkyl Propiolates Catalysed by Ph3P

2-Hydroxypyridine undergoes a smooth reaction with alkyl propiolates in the presence of triphenylphosphine (15 mol%) to produce the corresponding alkyl 2-[2-oxopyridin-1(2H)-yl]acrylates in good yields. When the reaction was performed by 2-hydroxyquinoline and 2-hydroxyisoquinoline similar α-substituted alkyl acrylates were obtained.

Novel multicomponent reactions of primary amines and alkyl propiolates with alloxan derivatives in water

A water-accelerated multicomponent synthesis of organic target molecules has been used as a key method for the preparation of novel barbiturate derivatives. The three-component condensation reactions of primary amines with alkyl propiolates in the presence of alloxan derivatives in water are developed as efficient and clean green synthetic procedures for the high-yielding preparation of alkyl 2-(5-hydroxy-2,4,6-trioxohexahydro-5-pyrimidinyl)-3-(alkyl or arylamino)-2-propenoates. The above synthetic protocol provides rapid access to novel and diversely substituted barbiturate derivatives.

A Facile Synthesis of Stable 1,4-Diionic Phosphorus Compounds in Aqueous Media

Stable phosphorus betaines are obtained from the 1:1:1 addition reaction between triphenylphosphine and alkyl propiolates in the presence of CH-acids, such as cyclohexane-1,3-dione or 5,5-dimethylcyclohexane-1,3-dione in THF/H2O (1:1) in good yields.

Preparation of Trivinylstannyl Complexes of Manganese and Rhenium

Trivinylstannyl complexes Re[Sn{C(COOR)═CH2}3](CO)2L3 (1, 2) and M[Sn{C(COOR)═CH2}3](CO)3L2 (3, 4) [M = Re, Mn; R = Me, Et; L = P(OEt)3, PPh(OEt)2] were prepared by allowing trihydridostannyl complexes Re(SnH3)(CO)2L3 and M(SnH3)(CO)3L2 to react with alkyl propiolates. The complexes were characterized spectroscopically (IR, 1H, 31P, 13C, 119Sn NMR) and by X-ray crystal structure determination of Re[Sn{C(COOMe)═CH2}3](CO)2[P(OEt)3]3 (1a). Reaction of trivinylstannyl complex 1a with HCl resulted in cleavage of one vinyl group to give (chlorodivinyl)stannyl derivative Re[SnCl{C(COOMe)═CH2}2](CO)2[P(OEt)3]3 (6a).

One-Pot Synthesis of Arylsulfonamides and Azetidine-2,4-diones via Multicomponent Reaction of an Amine, an Acetylenic Compound, and an Arylsulfonyl Isocyanate

An effective route to novel arylsulfonamides is described. It involves the reaction of an enamine derived from the addition of primary or secondary amines to acetylenecarboxylates (dialkyl acetylenedicarboxylates or alkyl propiolates) with an arylsulfonyl isocyanate. These arylsulfonamides show dynamic NMR behavior in solution. A different reactivity pattern was observed with the methyl 3-(diethylamino)acrylate. The latter, generated in situ from Et 2 NH and methyl propiolate, on reaction with an arylsulfonyl isocyanate afforded exclusively the azetidine-2,4-dione (malonimide-) derivatives in good yield. These malonimides also show dynamic NMR behavior in solution because of restricted rotation around the C-N bond resulting from conjugation of the side-chain N-atom with the adjacent α,β-unsaturated carbonyl group.

Synthesis of polyfunctionalized alkenes and α,β-unsaturated γ-lactams from the reaction of alkyl propiolates and CH-acids such as diethyl acetamidomalonate and ethyl acetamidocyanoacetate in the presence of triphenylphosphine

Dialkyl 1-(Z)-2-(acetylamino)-2-butenedioates, 1,1-diethyl-3-alkyl (E)-(1-acetylamino)-2-propene-1,1,3-tricarboxylate, 5-ethyl-1-methyl (E)-4-(acetylamino)-4-cyano-2-pentenedioate and ethyl 1-acetyl-2-cyano-5-oxo-2,5-dihydro-1H-pyrrole-2-carboxylate were obtained from the three-component reactions between alkyl propiolates and CH-acids such as diethyl acetamidomalonate and ethyl acetamidocyanoacetate in the presence of triphenylphosphine at room temperature in dry dichloromethane.

One-pot synthesis of functionalized thioureas by reaction of benzoyl isothiocyanates, secondary amines, and alkyl propiolates

An efficient one-pot synthesis of functionalized thioureas is described via three-component reaction of benzoyl isothiocyanates, secondary amines, and alkyl propiolates in the presence of triphenylphosphine (20 mol%).

The Novel One-Pot Synthesis of Functionalized Vinyl Sulfides Using Triphenylphosphine Catalyzed Nucleophilic Addition of Thiols to Acetylenes

3-mercapto-2-butanone undergoes a smooth reaction with electron-deficient symmetric and asymmetric acetylenes in the presence of catalytic amount of triphenylphosphine under neutral conditions to produce S-functionalized vinyl sulfides (Z/E isomers) in moderately high yields. Keywords: Triphenylphosphine, alkyl propiolate, organophosphorus compounds, vinyl sulfides

One‐Pot Synthesis of Functionalized Hydantoin Derivatives via a Four‐Component Reaction Between an Amine, an Arylsulfonyl Isocyanate and an Alkyl Propiolate or Dialkyl Acetylenedicarboxylate in the Presence of Triphenylphosphine.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Metal-Free Access to Fully Substituted Skipped Diynes. An Efficient Chemodifferentiating A2BB‘ 4CR Manifold

A metal-free chemodifferentiating A2BB' 4CR manifold for the modular synthesis of tertiary skipped diynes is described. The manifold performs a triethylamine triggered reaction of alkyl propiolates and acid chlorides to assemble two units of each component in the form of two propargylic alkynoates, a tertiary alcohol, and an ester. A differentiated incorporation of the two acid chloride components ensures functional diversity in the final structure. In addition, the presence of two connected propargylic alkynoates provides a reactive platform for complexity generation.

One-pot synthesis of functionalized hydantoin derivatives via a four-component reaction between an amine, an arylsulfonyl isocyanate and an alkyl propiolate or dialkyl acetylenedicarboxylate in the presence of triphenylphosphine

An effective route to functionalized hydantoin derivatives is described, involving the reaction of a urea derivative resulting from the addition of a primary amine to an arylsulfonyl isocyanate, and an alkyl propiolate or dialkyl acetylenedicarboxylate in the presence of triphenylphosphine. The reactive 1:1 intermediate obtained from the addition of triphenylphosphine to the alkyl propiolate or dialkyl acetylenedicarboxylate was trapped by NH-acids such as the urea derivative to produce functionalized hydantoin derivatives.

Transformations of 4,5,6,7-tetrahydrothieno[3,2-c]-and 1,2,3,4-tetrahydrobenzothieno[2,3-c]pyridines in reactions with alkynes activated by electron-withdrawing substituents

The transformations of tetrahydrothieno[3,2-c]-and tetrahydrobenzothieno[2,3-c]pyridines in the reactions with acetylenedicarboxylic ester, alkyl propiolates, and acetylacetylene in alcohols were studied. Tetrahydrobenzothieno[3,2-d]azocines and 2-methoxyethyl-3-vinyl-aminoethylbenzothiophenes were synthesized.

Synthesis of Stable Phosphorus Ylides by the Reaction of Ph3P With Activated Acetylenes in the Presence of Dimethyl Methoxymalonate

Triphenylphosphine reacts with dimethyl methoxymalonate in the presence of alkyl propiolates or dialkyl acetylenedicarboxylates to produce trialkyl 3-(1,1,1-triphenyl-λ5-phosphanylidene)-1-propene-1,1,2-tricarboxylates or tetraalkyl 3-(1,1,1-triphenyl-λ 5-phosphanylidene)-1-propene-1,1,2,3-tetracarboxylates in good yields.

Vinylphosphonium Salt Mediated Reaction Between Alkyl Propiolates and Aminophenols or Hydroxyphenols.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.