4437-80-3

Usage

Synthesis Reference(s)

Tetrahedron Letters, 30, p. 3981, 1989 DOI: 10.1016/S0040-4039(00)99300-6

InChI:InChI=1/C6H8O3/c1-4-6(2,3)9-5(7)8-4/h1H2,2-3H3

Upstream product

• 124-38-9 carbon dioxide 
• 115-19-5 2-methyl-but-3-yn-2-ol 
• 33060-69-4 2-methylbut-3-yn-2-yl carbamate 

Downstream Products

• 55476-05-6 3-(4-chlorophenyl)-5,5-dimethyl-4-methylidene-2-oxooxazolidine 
• 211933-20-9 Benzoic acid (E)-4-(1,1-dimethyl-2-oxo-propoxycarbonyloxy)-2-methyl-1-methylene-but-2-enyl ester 
• 91957-34-5 3-benzyl-5,5-dimethyl-4-methylene-2-oxazolidinone 
• 128457-29-4 3-benzyl-4-hydroxy-4,5,5-trimethyl-2-oxazolidinone 
• 151535-49-8 2,3,4,5,6-pentahydro-5-hydroxy-5,6,6-trimethyl-1,3,4-oxadiazin-2-one 
• 6268-43-5 1,3-di-pyridin-2-yl-urea 
• 340265-98-7 4-hydroxy-4,5,5-trimethyl-3-phenethyl-oxazolidin-2-one 
• 493-71-0 bullatenone 
• 115-22-0 3-Hydroxy-3-methyl-2-butanone 
• 108-32-7 1,2-propylene cyclic carbonate 

Relevant academic research and scientific papers

Gold(I)-catalyzed formation of 4-alkylidene-1,3-dioxolan-2-ones from propargylic tert-butyl carbonates

A study concerning the gold(I)-catalyzed rearrangement of propargylic tert-butyl carbonates into 4-alkylidene-1,3-dioxolan-2-ones is described. The mild reaction conditions employed allow the efficient synthesis of a variety of cyclic carbonates that would be less conveniently obtained using reported methods. Variability in the structure of the final product has been observed and is significantly dependent on the nature of the substituent attached to the alkyne moiety.

Catalytic formation of carbamates and cyclic carbonates by copper complex of 2,5,19,22-tetraaza[6,6](1,1′)ferrocenophane-1,5-diene X-ray crystal structure of [Cu(1)]PF6

The reaction of [Cu(MeCN)4]PF6 with a ferrocene-containing tetraazamacrocycle 2,5,19,22-tetraaza[6,6](1,1)ferrocenophane-1,5-diene (1) gives the copper(I) complex of the type [Cu(1)]PF6 (2) which crystallizes in the orthorhombic system: P212121 (#19); a = 7.597(2) A, b = 14.805(5) A, c = 24.194(4) A; Z = 4; R = 0.080; Rw = 0,083. The geometry around the central metal is a distorted tetrahedron with two pairs of differing Cu-N bond length. This complex has demonstrated the excellent catalytic activity toward the formation of cyclic carbonates and carbamates in the presence of CO2, giving almost quantitative product yields in most reactions that have been employed.

Nickel-Catalyzed CO2Rearrangement of Enol Metal Carbonates for the Efficient Synthesis of β-Ketocarboxylic Acids

4-Methylene-1,3-dioxolan-2-ones underwent oxidative addition of a Ni0catalyst in the presence of Me2Al(OMe), followed by a coupling reaction with alkynes, to form δ,?-unsaturated β-ketocarboxylic acids with high regio- and stereoselectivity. The reaction proceeds by [1,3] rearrangement of an enol metal carbonate intermediate and the formal reinsertion of CO2.

Cu(I)/ionic liquids promote the conversion of carbon dioxide into oxazolidinones at room temperature

Recently, the efficient chemical fixation of carbon dioxide (CO2) into high value chemicals without using noble metal catalysts has become extremely appealing from the viewpoint of sustainable chemistry. In this work, a one-pot three component reaction of propargylic alcohols, anines and CO2 that can proceed in an atom economy and environmentally benign manner by combination of CuI and tetrabutylphosphonium imidazol ([P4444][Im]) as a catalyst was described. Catalysis studies indicate that this catalytic system is an effective catalyst for the conversion of CO2 into oxazolidinones at room temperature and ambient pressure without any solvent. The results provide a useful way to design novel noble metal-free catalyst systems for the transformation of CO2 into other valuable compounds.

Ag Nanoparticles Supported on a Resorcinol-Phenylenediamine-Based Covalent Organic Framework for Chemical Fixation of CO2

Covalent organic frameworks are a new class of crystalline organic polymers possessing a high surface area and ordered pores. Judicious selection of building blocks leads to strategic heteroatom inclusion into the COF structure. Owing to their high surface area, exceptional stability and molecular tunability, COFs are adopted for various potential applications. The heteroatoms lining in the pores of COF favor synergistic host–guest interaction to enhance a targeted property. In this report, we have synthesized a resorcinol-phenylenediamine-based COF which selectively adsorbs CO2 into its micropores (12 ?). The heat of adsorption value (32 kJ mol?1) obtained from the virial model at zero-loading of CO2 indicates its favorable interaction with the framework. Furthermore, we have anchored small-sized Ag nanoparticles (≈4–5 nm) on the COF and used the composite for chemical fixation of CO2 to alkylidene cyclic carbonates by reacting with propargyl alcohols under ambient conditions. Ag@COF catalyzes the reaction selectively with an excellent yield of 90 %. Recyclability of the catalyst has been demonstrated up to five consecutive cycles. The post-catalysis characterizations reveal the integrity of the catalyst even after five reaction cycles. This study emphasizes the ability of COF for simultaneous adsorption and chemical fixation of CO2 into corresponding cyclic carbonates.

CO2-Sourced α-Alkylidene Cyclic Carbonates: A Step Forward in the Quest for Functional Regioregular Poly(urethane)s and Poly(carbonate)s

Described is a robust platform for the synthesis of a large diversity of novel functional CO2-sourced polymers by exploiting the regiocontrolled ring-opening of α-alkylidene carbonates by various nucleophiles. The reactivity of α-alkylidene carbonates is dictated by the exocyclic olefinic group. The polyaddition of CO2-sourced bis(α-alkylidene carbonate)s (bis-αCCs) with primary and secondary diamines provides novel regioregular functional poly(urethane)s. The reactivity of bis-αCCs is also exploited for producing new poly(β-oxo-carbonate)s by organocatalyzed polyaddition with a diol. This synthesis platform provides new functional variants of world-class leading polymer families (polyurethanes, polycarbonates) and valorizes CO2 as a chemical feedstock.

Room-Temperature Synthesis of a Hollow Microporous Organic Polymer Bearing Activated Alkyne IR Probes for Nonradical Thiol-yne Click-Based Post-Functionalization

This work shows that hollow microporous organic polymer (H-MOP-A) with activated internal alkynes as IR probes can be prepared by template synthesis based on acyl Sonogashira-Hagihara coupling at room temperature. The H-MOP-A is a versatile platform in the main chain PSM based on nonradical thiol-yne click reaction. Moreover, an IR peak of internal alkynes in the H-MOP-A is very intense and could be utilized in the monitoring of thiol-yne click-based main chain PSM. The functionalized H-MOP-A with carboxylic acids (H-MOP-CA) showed efficient adsorption toward Ag+ ions. The resultant H-MOP-CA-Ag showed excellent performance in the CO2 fixation to α-alkylidene cyclic compounds.

Synthesis Cu(I)–CN-based MOF with in-situ generated cyanogroup by cleavage of acetonitrile: Highly efficient for catalytic cyclization of propargylic alcohols with CO2

Developing a highly effective process for synthesis a cyano-bridged compound to avoid toxic organic or inorganic cyanides is very significant method for alleviating cyanides pollution. Here, a CN-based MOF catalyst (Cu(I)–CN–BPY) was synthesized by using copper ions coupled with Na4W10O32 in CH3CN under solvothermal conditions. The cyano-groups are generated in situ from the cleavage of C(sp3)–C(sp) in CH3CN. Because Cu(I) sites have ability to activate π-activate internal alkynes of carbon–carbon triple bonds for carboxylic cyclization reactions, which was applied in the cyclization of propargylic alcohols with CO2 and exhibited high efficiency with >95 % yields. For seeking out the active sites of MOF structure in carboxylic cyclization, we also synthesized two MOFs of Cu(I)–Cl–BPY and Cu(I)–I–BPY, and investigated for this reaction.

PHOSPHINE CATALYSED SYNTHESIS OF UNSATURATED CYCLIC CARBONATES FROM CARBON DIOXIDE AND PROPARGYLIC ALCOHOLS

A new route to α-methylene cyclic carbonates is reported, by direct reaction of carbon dioxide with α-ethynyl alcohols in the presence of a catalytic amount of a phosphine.

Copper-catalysed synthesis of α-alkylidene cyclic carbonates from propargylic alcohols and CO2

We report a N-heterocyclic carbene copper(i) complex-catalysed formal cycloaddition between readily available propargylic alcohols and carbon dioxide at room temperature. By using the combination of a sterically demandingBPDPrCuCl complex (BPDPr = 1,3-bis(2,6-diisopropylphenyl)-1,3-diazonine-2-ylidene) and CsF, as catalytic system, primary propargylic alcohols are efficiently converted to the corresponding α-alkylidene cyclic carbonates. Gram scale (up to 89% yield) and reusability experiments (74% global yield, turnover number value = 103) showcase the robustness of the catalytic system. This practically simple protocol also tolerates secondary and tertiary propargylic alcohols under CO2at atmospheric pressure, enabling the direct synthesis of substituted and unsubstituted α-alkylidene cyclic carbonates at room temperature.