547-65-9Relevant articles and documents
Precursor of α-methylene-γ-butyrolactone involved in the insecticidal activity of thunberg spiraea, Spiraea thunbergii
Kim, Chul-Sa,Datta, Probal Kanti,Hara, Tetsuro,Itoh, Eiji,Horiike, Michio
, p. 152 - 154 (1999)
6-Tuliposide A {6-O-(4-hydroxy-α-methylenebutyryl)-D-glucopyranose} was isolated from thunberg spiraea (Spiraea thunbergii) leaves. Acid-hydrolysis of this compound generated tulipalin A (α-methylene-γ-butyrolactone). This compound is thus considered as a precursor of insecticidal tulipalin A.
Bicomponent transparent polyester networks with shape memory effect
Zhou, Jiawen,Schmidt, Annette M.,Ritter, Helmut
, p. 939 - 942 (2010)
Elastic bicomponent networks with shape memory effect were obtained via cross-linking reactions of unsaturated polyester with methacrylates. Unlike conventional shape memory polymers, the new material is transparent, rubbery, and can be tailored to various transition temperatures by macromolecular engineering. Various unsaturated copolymers of α-methylene-γ- butyrolactone and ε-caprolactone were synthesized by ring-opening mechanism. Depending on the composition of the unsaturated polyester materials, their mechanical properties and glass transition temperature were varied.
Diastereoselective Alkene Hydroesterification Enabling the Synthesis of Chiral Fused Bicyclic Lactones
Shi, Zhanglin,Shen, Chaoren,Dong, Kaiwu
supporting information, p. 18039 - 18042 (2021/11/16)
Palladium-catalysed diastereoselective hydroesterification of alkenes assisted by the coordinative hydroxyl group in the substrate afforded a variety of chiral γ-butyrolactones bearing two stereocenters. Employing the carbonylation-lactonization products as the key intermediates, the route from the alkenes with single chiral center to chiral THF-fused bicyclic γ-lactones containing three stereocenters was developed.
Ligand-Controlled Palladium-Catalyzed Carbonylation of Alkynols: Highly Selective Synthesis of α-Methylene-β-Lactones
Beller, Matthias,Ge, Yao,Jackstell, Ralf,Jiao, Haijun,Liu, Jiawang,Spannenberg, Anke,Yang, Ji,Ye, Fei
supporting information, p. 21585 - 21590 (2020/09/23)
The first general and regioselective Pd-catalyzed cyclocarbonylation to give α-methylene-β-lactones is reported. Key to the success for this process is the use of a specific sterically demanding phosphine ligand based on N-arylated imidazole (L11) in the presence of Pd(MeCN)2Cl2 as pre-catalyst. A variety of easily available alkynols provide under additive-free conditions the corresponding α-methylene-β-lactones in moderate to good yields with excellent regio- and diastereoselectivity. The applicability of this novel methodology is showcased by the direct carbonylation of biologically active molecules including natural products.
Novel multi-dentate phosphines for Pd-catalyzed alkoxycarbonylation of alkynes promoted by H2O additive
Yang, Da,Liu, Lei,Wang, Dong-Liang,Lu, Yong,Zhao, Xiao-Li,Liu, Ye
, p. 236 - 244 (2019/02/19)
A series of novel multi (bi-/tri-/tetra-)-dentate phosphines with good robustness against water and oxygen were synthesized and fully characterized. It was found that the developed ionic tri-dentate phosphine (L2′) enabled Pd-catalyzed alkoxycarbonylation of alkynes most efficiently while H2O was used as an additive instead of acid. As for L2′, its unique steric configuration with two types of potential P-P chelation modes (P?P distance of 4.31 ? and 4.36 ? respectively) to Pd-centre rendered the corresponding Pd-catalyst high activity and good stability for alkoxycarbonylation of alkynes. The in situ FT-IR analysis also verified that the formation and stability of Pd–H active species were greatly facilitated with the presence of L2′ as well as H2O additive. In addition, as an ionic phosphine, L2′ based PdCl2(MeCN)2 system immobilized in RTIL of [Bmim]NTf2 could be recycled for 7 runs without obvious activity loss or metal leaching.
MANUFACTURING METHOD OF α-METHYLENE-γ-BUTYROLACTONE
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Paragraph 0047-0050, (2018/08/19)
PROBLEM TO BE SOLVED: To provide a method capable of manufacturing high purity α-methylene-γ-butyrolactone at high yield. SOLUTION: α-methylene-γ-butyrolactone is manufactured by reacting oxalate ester and alcoholate with γ-butyrolactone to synthesize α-oxalyl-γ-butyrolactone, neutralizing them by acid and then reacting an enol salt of the α-oxalyl-γ-butyrolactone, formaldehyde or a precursor generating formaldehyde and carbonate. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT
Synthesis of methylene butyrolactone polymers from itaconic acid
Trotta, Jacob T.,Jin, Mengyuan,Stawiasz, Katherine J.,Michaudel, Quentin,Chen, Wei-Liang,Fors, Brett P.
, p. 2730 - 2737 (2017/07/25)
Herein, we report the transformation of β-monomethyl itaconate, an inexpensive and biorenewable alternative to petroleum feedstocks, to the high-value monomer α-methylene-γ,γ-dimethyl-γ-butyrolactone (Me2MBL) through a selective addition strategy. This strategy is also applied to the synthesis of α-methylene-γ-butyrolactone (MBL, tulipalin A), a monomer that can be polymerized to give materials with desirable properties (high decomposition temperature, glass transition temperature, and refractive index). Subsequent polymerization of both Me2MBL and MBL through reversible addition-fragmentation chain-transfer polymerization generates well-defined poly(Me2MBL) and poly(MBL) (PMBL). Physical characterization of poly(Me2MBL) shows good physical properties comparable with known PMBL materials.
Enzymatic synthesis of optically active lactones via asymmetric bioreduction using ene-reductases from the old yellow enzyme family
Turrini, Nikolaus G.,Hall, Mélanie,Faber, Kurt
, p. 1861 - 1871 (2015/06/02)
In contrast to the widely studied asymmetric bioreduction of α,β-unsaturated carboxylic acid esters catalyzed by ene-reductases, the reaction applied to lactones remains unexplored. A broad set of ene-reductases was found to reduce various α-, β- and γ-substituted α,β-unsaturated butyrolactones to yield the corresponding saturated non-racemic lactones. Substitution patterns greatly influenced activities and stereoselectivities and lactone products were obtained in moderate to excellent yields; importantly, enzyme-based stereocontrol allowed access to both enantiomers in up to >99% ee. Chiral recognition of a distant γ-center led to kinetic resolution with remarkable enantioselectivities (E values up to 49). An unprecedented case of dynamic kinetic resolution was observed with 3-methyl-5-phenylfuran-2(5H)-one, whereby spontaneous racemization of the substrate furnished the product in up to 73% conversion and >99% ee and 96% de.
Production Method of a-Methylene Lactone
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Paragraph 0058; 0061; 0042, (2015/03/16)
The present invention relates to a production method of α-methylene lactone which comprises the following steps: (A) a step of producing an enolate intermediate by making lactone react with alkyl formate under the presence of an alkoxide base; and (B) making the enolate intermediate react with paraformaldehyde. The production method of the present invention is capable of reducing the process time, improving yield, and minimizing the contamination of a reactor.
4-(Dimethylamino)pyridine as a catalyst for the lactonization of 4-hydroxy-2-methylenebutanoate esters
Nicponski, Daniel R.
supporting information, p. 2075 - 2077 (2014/04/03)
The catalytic action of 4-(dimethylamino)pyridine (DMAP) in lactonizing 4-hydroxy-2-methylenebutanoate esters to 2-methylene-γ-butyrolactones is described. The use of DMAP, which functions as an excellent complement to the more traditional acid-catalyzed lactonization protocol, allows for the synthesis of 2-methylene-γ-butyrolactones containing acid-sensitive groups under essentially neutral conditions.
