Entrapment of cyclopentadiene in zeolite NaY and its application for solvent-free Diels-Alder reactions in the nanosized confined environment

Nonpolar cyclopentadiene was stably entrapped as a monomer in the hydrophilic supercages of zeolite NaY. A monomer form of cyclopentadiene in the supercages was confirmed by ¹³C MAS NMR spectroscopy. The adsorbed cyclopentadiene in the confined cavities performed the Diels-Alder reaction with typical dienophiles under solvent-free conditions more effectively than in organic and water media.     

Synthesis of 5-vinyl-2-norbornene through Diels-Alder reaction of cyclopentadiene with 1, 3-butadiene in supercritical carbon dioxide

An efficient method for the synthesis of 5-vinyl-2-norbornene from cyclopentadiene and 1,3-butadiene was developed.The Diels-Alder reaction of cyclopentadiene with 1,3-butadiene proceeded smoothly in supercritical carbon dioxide in the absence of any polymerization inhibitor to produce the corresponding 5-vinyl-2-norbornene in satisfactory yield with high selectivity.     

Diels-Alder Addition of Dicyclopentadiene with Cyclopentadiene in Polar Solvents

Diels-Alder addition of dicyclopentadiene and cyclopentadiene in polar solvents has been studied to produce tricyclopentadiene（TCPD） that is a potential high-density fuel precursor. GC and MS analysis shows that the adducts contain two isomers, namely exo- and endo-TCPD. Theoretical simulation shows that although the transition state of endo-TCPD has a lower activation energy, exo-TCPD is thermodynamically preferred. Polar solvents can accelerate the reaction rate and improve the exo/endo ratio of TCPD because the transition state of exo-TCPD has a higher polarity than that of endo-TCPD. The solvent effect follows the order of polarity： benzyl methanol〉cyclohexanone〉toluene. The conversion rises when the temperature ranges from 120 to 150 ℃, but the selectivity of TCPD slightly decreases. Increasing the pressure can improve the conversion but the exo/endo ratio of TCPD is unchanged. The apparent kinetics in different solvents was determined via nonlinear regression. The activation energies are 99.47, 101.15, and 107.32 kJ/mol for benzyl methanol, cyclohexanone, and toluene, respectively. The optimal reaction conditions are as follows： benzyl methanol as solvent, temperature 150 ℃, and pressure 900 kPa. After an 11-hour reaction, a conversion of 58.0%, a TCPD selectivity of 95.7%, and an exo/endo ratio of 1/5.3 has been obtained.     

应用Diels-Alder反应制备聚合物的研究进展

由于Diels-Alder反应具有一系列重要特点(原子经济性、热可逆性、立体选择性、立体专一性和区域选择性等),自从1928年被发现以来,该反应就一直是人们研究的热点。将其应用于聚合物的合成中,可制备一些具有特殊性能的Diels-Alder聚合物,人们在这方面作了大量的研究工作,取得了许多研究成果。本文首先根据不同的分类标准,对应用Diels-Alder反应制备聚合物的研究进行了分类,然后结合本课题组的相关研究工作,综述了近年来人们在该领域的研究进展,最后展望了其研究前景。     

Synthesis and Diels-Alder reaction of a sapphyrin derivative

Sapphyrins participate in Diels-Alder reactions with pentacene affording novel barrelene-fused sapphyrins. The new compounds were synthesized using traditional heating and microwave irradiation conditions. The experiments carried out under microwave irradiation proved cleaner, affording only the monoadduct and in higher yields.     

Synthesis and thermolysis of a Diels-Alder adduct of pentacene and thiophosgene

Pentacene has excellent semi-conducting properties but its practical use in organic thin film transistors (OTFTs) gives rise to a lot of problems caused by its sensitivity to oxygen and its very low solubility. In order to solve the problems involved in the use of pentacene, we have synthesized a Diels-Alder adduct of pentacene with thiophosgene.     

亚胺参与的Diels-Alder反应及其在生物碱全合成中的应用

在通过Diels-Alder反应建立各种含氮六员环的反应中,亚胺是一个最有用的亲双烯试剂。该法应用简便、并显示出较好的位置选择性和立体选择性。对其在生物碱类合成中的应用也作了综述。     

Perfluoroacetylenephosphonates in Diels-Alder reactions: Synthesis of perfluoroalkylated heterocyclic and carbocyclic phosphonates

Diethyl 3,3,3-trifluoroprop-1-ynylphosphonate and diethyl 3,3,4,4,4-pentafluorobut-1-ynylphosphonate are obtained by the dehydration of the corresponding enols using P₂O₅-Et₃N system as a dehydrating agent, affording acetylenes in 50-60% yield. By the reaction of these perfluoroacetylenephosphonates with acyclic and cyclic 1,3-dienes or diene-like heteroaromatic and aromatic compounds corresponding Diels-Alder cyclo- and bicycloadducts were prepared in good yields (65-90%). The reactivity of the dienes and acetylenes which depends on their structure, as well as the regioselectivity of the reaction are established.     

Photo-RAFT Polymerization for Hydrogel Synthesis through Barriers and Development of Light-Regulated Healable Hydrogels under NIR Irradiation

We report an aqueous and near-infrared (NIR) light mediated photoinduced reversible addition–fragmentation chain transfer (photo-RAFT) polymerization system catalyzed by tetrasulfonated zinc phthalocyanine (ZnPcS₄⁻) in the presence of peroxides. Taking advantage of its fast polymerization rates and high oxygen tolerance, this system is successfully applied for the preparation of hydrogels. Exploiting the enhanced penetration of NIR light, photoinduced gelation is effectively performed through non-transparent biological barriers. Notably, the RAFT agents embedded in these hydrogel networks can be reactivated on-demand, enabling the hydrogel healing under NIR light irradiation. In contrast to the minimal healing capability (<15 %) of hydrogels prepared by free radical polymerization (FRP), RAFT-mediated networks display more than 80 % recovery of tensile strength. Although healable polymer networks under UV and blue lights have already been established, this work is the first photochemistry system using NIR light, facilitating photoinduced healing of hydrogels through thick non-transparent barriers.     

水凝胶的制备及仿生设计在能源领域应用的研究进展

能源与环境问题是当前时代面临的一大课题,有效利用并储存能源,缓解一系列严峻的环境污染问题也是当前研究的热点,电化学储能、光催化、光热界面蒸发和水汽收集这些能源利用措施已经作为环保手段深入人类的生活.大自然作为一位天然的设计师为我们能够提供诸多灵感,自然界诸多生物、生命体系中特性、机制和结构均暗含着十分巧妙的奥秘.本文重...     

Synthesis of a simple chiral auxiliary derived from levoglucosenone and its application in a Diels-Alder reaction

The synthesis of a chiral alcohol derived from levoglucosenone has been studied. The alcohol was employed as chiral template in an asymmetric Diels-Alder reaction of the corresponding acrylic ester derivative with cyclopentadiene, and was shown to be an efficient asymmetric inductor. The oxidation reaction detected during the hydrogenation of a secondary allylic alcohol intermediate with Pd/C was also investigated.     

Design and Synthesis of a Calcium‐Sensitive Photocage

Photolabile protecting groups (or “photocages”) enable precise spatiotemporal control of chemical functionality and facilitate advanced biological experiments. Extant photocages exhibit a simple input–output relationship, however, where application of light elicits a photochemical reaction irrespective of the environment. Herein, we refine and extend the concept of photolabile groups, synthesizing the first Ca²⁺‐sensitive photocage. This system functions as a chemical coincidence detector, releasing small molecules only in the presence of both light and elevated [Ca²⁺]. Caging a fluorophore with this ion‐sensitive moiety yields an “ion integrator” that permanently marks cells undergoing high Ca²⁺ flux during an illumination‐defined time period. Our general design concept demonstrates a new class of light‐sensitive material for cellular imaging, sensing, and targeted molecular delivery.     

A Diels-Alder Reaction Conducted Within the Parameters of Aqueous Organocatalysis: Still Just Smoke and Mirrors

Conducting reactions using water as solvent is a highly prized goal for the organic chemist. Based upon recent literature and our continuing interest in the field of aqueous organocatalysis, we tested the scope of an enamine based Diels-Alder reaction using (±)-nornicotine, proline, and a proline derivative as aqueous organocatalysts. Unfortunately, none of the examined catalysts under aqueous conditions proved useful, leaving the aqueous Diels-Alder reaction as an elusive goal.     

Synthesis of 2-Acyl-2H-1,2,3-diazaphospholes and Their Diels-Alder Reaction with Cyclopentadiene

2H-1,2,3-Diazaphospholes 3a-3h were prepared from various ketone acylhydrazones and phosphorus trichloride in the presence of triethylamine. Compounds 3 underwent feasible hetero-Diels-Alder reactions with cyclopentadiene to afford the respective anellated [1,2,3]diazaphospholes 4a--4d as well as 4a‘--4d‘ in moderate yields. The endo rule in the reaction was observed under kinetic control conditions.     

Synthesis and Diels-Alder reactions of 9-(4-benzyloxazolin-2-yl) anthracene

The synthesis of 9-(4-benzyloxazolin-2-yl)anthracene is described employing a new approach for the cyclisation of β-hydroxy amides to oxazolines. Thermal Diels-Alder reactions with N-methyl maleimide were found to be considerably slower than those previously observed. Essentially no diastereoselectivity was observed in these reactions as the benzyl stereodirecting group is remote from the reactive site. Minor rate enhancements were noticeable in the presence of some added Lewis acids, but with no diastereoselection.     

Direct Synthesis of Biodegradable Polysaccharide Derivative Hydrogels Through Aqueous Diels‐Alder Chemistry

A robust synthetic strategy where polysaccharide derivative precursors react through aqueous Diels–Alder chemistry without the involvement of catalysts and coupling reagents, allowing for the direct encapsulation of positive and negative proteins within biodegradable hydrogels. The results demonstrated that the aqueous Diels–Alder chemistry provides an extremely selective reaction and proceeds with high efficiency for polysaccharide bioconjugation. This synthetic approach uniquely allows for the direct fabrication of biologically functionalized gels with ideal structures, which provides a competitive alternative to conventional conjugation techniques such as click chemistry.

     

Aqueous Diels-Alder Reactions of Cyclopentadicnc with Symmetric Diester of Fumarate or Maleate

Cis- or irans- dimethyl and diethyl ester of bicyclo[2,2,1]hept-5-ene-2,3-die(2 or 4) were used as pesticides 1-4 in the fourties and fifties of the century to prevent orkill mosquito, fly and flea. The of's-dimethyl ester Za was also added to cosmetics forthe same purpose 5. The diethyl and dipropyl esters (2b and Zc) could be used to makerubber and elastomers6'7. Besides, this kind of compounds are important intermediatesfor synthesis of some drugs.The Diels-Alder reaction of cyclopentadie…     

Synthesis of 2,4-disubstituted 3-chlorofurans and the effect of the chlorine substituent in furan Diels-Alder reactions

2,4-Disubstituted 3-chlorofurans were synthesized in 42-69% overall yields by CuCl/bpy-catalyzed halogen atom transfer radical cyclization of 1-substituted 2,2,2-trichloroethyl allyl ethers to 2-substituted 3,3-dichloro-4-(1-chloroalkyl)tetrahydrofurans followed by base promoted dehydrochlorination. Diels-Alder reactions of 4-substituted 2-(2-furyl)-, 2-styryl-, and 2-crotyl-3-chlorofurans with dimethyl acetylenedicarboxylate occurred exclusively on the chlorofurano diene moieties and not on the non-chlorinated furano diene or the chlorinated exocyclic diene alternatives, demonstrating the predominance of the halogen effect in the furan Diels-Alder reaction.     

Dynamic Exchange in 3D Cell Culture Hydrogels Based on Crosslinking of Cyclic Thiosulfinates

Dynamic polymer materials are highly valued substrates for 3D cell culture due to their viscoelasticity, a time-dependent mechanical property that can be tuned to resemble the energy dissipation of native tissues. Herein, we report the coupling of a cyclic thiosulfinate, mono-S-oxo-4-methyl asparagusic acid, to a 4-arm PEG-OH to prepare a disulfide-based dynamic covalent hydrogel with the addition of 4-arm PEG-thiol. Ring opening of the cyclic thiosulfinate by nucleophilic substitution results in the rapid formation of a network showing a viscoelastic fluid-like behaviour and relaxation rates modulated by thiol content through thiol-disulfide exchange, whereas its viscoelastic behaviour upon application as a small molecule linear crosslinker is solid-like. Further introduction of 4-arm PEG-vinylsulfone in the network yields a hydrogel with weeks-long cell culture stability, permitting 3D culture of cell types that lack robust proliferation, such as human pluripotent stem cell-derived cardiomyocytes (hPSC-CMs). These cells display native behaviours such as cell elongation and spontaneous beating as a function of the hydrogel's mechanical properties. We demonstrate that the mode of dynamic cyclic thiosulfinate crosslinker presentation within the network can result in different stress relaxation profiles, opening the door to model tissues with disparate mechanics in 3D cell culture.     

Diels-Alder modification of monoterpenes and Alder-ene synthesis involving 3-methyl-3-cyanocyclopropene

Monoterpene derivatives with a cyclopropane moiety in the molecule were prepared by reactions of 3-methyl-3-cyanocyclopropene with several monoterpenes and terpenoids (β-myrcene, neoalloocimene, alloocimene, β-pinene, carvone). They were formed using the Diels-Alder reaction, Alder-ene synthesis, conjugated Alder-ene addition, and Diels-Alder cyclization. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 350–353, July–August, 2006.