4-(Dimethylamino)pyridine as a catalyst for the lactonization of 4-hydroxy-2-methylenebutanoate esters

Nicponski, Daniel R.

doi:10.1016/j.tetlet.2014.02.024

Cited by 10 publications

(4 citation statements)

References 40 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…New well-resolved signals in the region for a methylene double bond at 5.6 and 6.2 ppm appeared (Figure S1). These signals are related to ring-opening MBL derivatives with the retention of a vinyl double bond and are related to isopropyl 4-hydroxy-2-methylene butanoate 54 in 25% conversion and dimers and/or trimers in approximately 8% conversion.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Functional Polyesters with Pendant Double Bonds Prepared by Coordination–Insertion and Cationic Ring-Opening Copolymerizations of ε-Caprolactone with Renewable Tulipalin A

et al. 2018

View full text Add to dashboard Cite

The synthesis of functional copolyesters that contain pendant double bonds in their structures is reported by ring-opening copolymerization of renewable monomer Tulipalin A (α-methylene-γ-butyrolactone, MBL) and ε-caprolactone (CL) using either coordination–insertion or monomer activated mechanisms. Aluminum tris(isopropoxide) (Al(OiPr)3) was successfully used as a cheap and commonly available catalyst for the coordination–insertion ring-opening copolymerization, and functional copolyesters with dispersities below 1.2 and with contents of MBL units in the copolymer up to 25 mol % were prepared. In addition, linear or multiarm copolymers of MBL with CL were synthesized by cationic ring-opening copolymerization that was conducted using protic acid as a “metal-free” catalyst in combination with mono- or multihydroxyl alcohols as initiators. The molecular characteristics and composition of the functional copolyesters were determined by GPC, NMR, two-dimensional NMR, and MALDI-TOF spectroscopy. The effect of MBL content on thermal properties of the copolyesters was investigated using DCS and TGA analyses. The availability of resulting functional copolyesters containing pendant double bonds toward postfunctionalization was demonstrated by either thermal or photochemical thiol–ene reactions with benzothioxanthene fluorophore or N-acetylcysteine, respectively.

show abstract

Section: ■ Results and Discussionmentioning

confidence: 99%

Functional Polyesters with Pendant Double Bonds Prepared by Coordination–Insertion and Cationic Ring-Opening Copolymerizations of ε-Caprolactone with Renewable Tulipalin A

et al. 2018

View full text Add to dashboard Cite

show abstract

“…Nevertheless, we were able to pick two crystals from the sample, which provided enantioenriched material [ee=50 and 98% for the ( S )‐enantiomer] and whose structures were determined by the means of X‐ray diffraction (for details see ESI). Additionally we found that under basic conditions 8 o lactonizes without any racemization [21] . By crystallization of the obtained lactone ( R )‐ 10 o and resubjecting the single crystals from the X‐ray analyses to HPLC‐UV analysis on a chiral stationary phase we were able to confirm the switch in enantiopreference of the catalyst compared to the initial report (see Scheme 3b and ESI).…”

Section: Methodsmentioning

confidence: 53%

“…Additionally we found that under basic conditions 8 o lactonizes without any racemization. [21] By crystallization of the obtained lactone ( R )‐ 10 o and resubjecting the single crystals from the X‐ray analyses to HPLC‐UV analysis on a chiral stationary phase we were able to confirm the switch in enantiopreference of the catalyst compared to the initial report (see Scheme 3 b and ESI). In order to identify the origin of the switch we reacted 4‐bromoacetophenone with the lactone based reagent 18 from our initial report (see Scheme 3 d).…”

mentioning

confidence: 70%

Asymmetric Allylation Catalyzed by Chiral Phosphoric Acids: Stereoselective Synthesis of Tertiary Alcohols and a Reagent‐Based Switch in Stereopreference

et al. 2021

View full text Add to dashboard Cite

The substrate scope of the asymmetric allylation with zinc organyls catalyzed by 3,3‐bis(2,4,6‐triisopropylphenyl)‐1,1‐binaphthyl‐2,2‐diyl hydrogenphosphate (TRIP) has been extended to non‐cyclic ester organozinc reagents and ketones. Tertiary chiral alcohols are obtained with ee's up to 94% and two stereogenic centers can be created. Compared to the previous lactone reagent the stereopreference switches almost completely, proving the fact that the nature of the organometallic compound is of immense importance for the asymmetry of the product.

show abstract

“…4-Dimethylaminopyridine (DMAP), a high-performance catalyst, has been broadly applied in organic synthesis, for example, esterification reactions, − Baylis–Hillman reactions, − multicomponent reactions, , etc. However, homogeneous catalysis has its intrinsic disadvantage of difficult separation of the catalyst, which will cause resource consumption and environmental pollution.…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient Polyacrylonitrile Fiber Catalysts Functionalized by Aminopyridines for the Synthesis of 3-Substituted 2-Aminothiophenes in Water

Xie

et al. 2016

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

Four aminopyridine (AP) functionalized polyacrylonitrile fibers (PANAPFs) were developed. UV–vis, FTIR, EA, and SEM were used to demonstrate the successful preparation of the fiber catalysts. Among the prepared catalysts, the PANp‑AP‑3F (with a C3 chain linker) and PANp‑AP‑6F (with a C6 chain linker) exhibited the best catalytic activity to efficiently catalyze the Gewald reaction of ethyl cyanoacetate and 2,5-dihydroxy-1,4-dithiane in water with yields up to 92% under a low catalyst dosage of 1 mol %. The influences of the position and length of the linker, i.e., the carbon chain between the fiber backbone and the aminopyridine moiety, on the catalytic activities were investigated in detail. In addition, the selected catalyst PANp‑AP‑3F was applied to the Gewald reaction of a series of active nitriles and 2,5-dihydroxy-1,4-dithiane and reused without further treatments. A possible mechanism and a microenvironment promoting process were conceived to explain the excellent catalytic properties of this catalytic system. Furthermore, the PANp‑AP‑3F performed well in a scaled-up experiment indicating its potential application in industry.

show abstract

4-(Dimethylamino)pyridine as a catalyst for the lactonization of 4-hydroxy-2-methylenebutanoate esters

Cited by 10 publications

References 40 publications

Functional Polyesters with Pendant Double Bonds Prepared by Coordination–Insertion and Cationic Ring-Opening Copolymerizations of ε-Caprolactone with Renewable Tulipalin A

Functional Polyesters with Pendant Double Bonds Prepared by Coordination–Insertion and Cationic Ring-Opening Copolymerizations of ε-Caprolactone with Renewable Tulipalin A

Asymmetric Allylation Catalyzed by Chiral Phosphoric Acids: Stereoselective Synthesis of Tertiary Alcohols and a Reagent‐Based Switch in Stereopreference

Highly Efficient Polyacrylonitrile Fiber Catalysts Functionalized by Aminopyridines for the Synthesis of 3-Substituted 2-Aminothiophenes in Water

Contact Info

Product

Resources

About