担载液相催化剂的研究——Ⅳ.催化剂的原位红外光谱表征

本文利用原位红外光谱方法对铑基担载液相催化剂(SLPC)在接近于实际反应条件下进行了表征。结果表明,新鲜催化剂上,铑膦络合物主要以二聚物的形式存在,如Rh_2(CO)_2(PPh_3)_4而在合成气或反应气氛中,催化剂铑膦络合物以单核络合物HRh(CO)_2(PPh_3)_2的形式存在。文中还对SLPC在CO,H_2,C_2-H_4,空气和HCl中处理时铑络合物种的变化进行了原位观察。实验结果表明,SLPC上活性铑络合物与对应的均相过程完全一致,进一步证实了SLPC催化在微观上就是一个均相催化过程。     

担载液相催化剂的研究——Ⅴ. 担载液相催化剂的EXAFS表征

本文利用EXAFS(Extended X-ray Absorption Fine Structure)对铑基担载液相催化剂(Supported Liquid Phase Catalyst SLPC)进行了结构表征。采用球面波理论对SLPC的EXAFS结果进行了多参数拟合。结果表明,在新鲜催化剂上,铑络合物以二聚物形式存在,推测其结构为(PPh_3)_2(CO)Rh-Rah(CO)(PPh_3)_2,Rh-C-O偏离共线分布。在经过羰化反应活化的活性SLPC上,铑络合物为单核的HRh(CO)_2(PPh_3)或Rh(CO)_2(PPh_32)_3。文中还讨论了SLPC的XRD谱。     

Indium Trichloride (InCl3) Catalyzed Synthesis of Fused 7‐Azaindole Derivatives Using Domino Knoevenagel‐Michael Reaction

An efficient and high yielding methodology developed for the synthesis of fused 7‐azaindole derivatives via one pot multicomponent assembly process of cyclic 1,3‐dicarbonyls with substituted aldehydes and 5‐amino‐1‐tert‐butyl‐1H‐pyrrole‐3‐carbonitrile. The transformation occurs via domino Knoevenagel‐ Michael reaction followed by intramolecular cyclization in the presence of catalytic amount of InCl₃ (10 mol %). Mild reaction conditions, easy isolation of products, and good to excellent yields in a shorter period of time are the silent features of present methodology. Structures of all the newly prepared compounds have been corroborated by various spectroscopic methods.     

A catalyst-and solvent-free multicomponent synthesis of 7-azagramine analogues via a Mannich type reaction

A catalyst-and solvent-free protocol for the synthesis of 7-azagramine analogues is described via a three-component Mannich type reaction between 7-azaindole, aromatic aldehydes and heterocyclic amines in acceptable to excellent yields. Structures of the compounds were confirmed satisfactorily by ¹H NMR, IR, mass, TOCSY, HSQC and HMBC spectral analyses.     

Ultrasound-Mediated Synthesis of Sulfonyl Urea Derivatives and Their In Vitro Antiproliferative Activity

Russian Journal of Organic Chemistry - A series of novel sulfonyl urea derivatives were designed as potential anticancer agents. These compounds were prepared in good yields by the reaction of...     

Microwave Promoted One‐Pot Synthesis of Some Novel N‐Aryl Isoquinoline Derivatives

Homophthalic anhydride 1 reacts with different aromatic amines to produce N‐substituted homophthalimides 2 under microwave irradiation. A rapid microwave‐assisted chemical synthesis of condensed 4‐substituted furo[2,3‐c]isoquinoline‐1,5(2H,4H)‐diones 3 and 5‐substituted‐2,3‐dihydro‐1H‐pyrano[2,3‐c]isoquinoline‐1,6(5H)‐diones 4 involving the condensation of a variety of alkanoyl chlorides with 2‐arylisoquinoline‐1,3‐diones 2 in the presence of base and aprotic solvent is described for the first time. By contrast, the facile ring opening reaction of furo[2,3‐c]isoquinoline‐1,5(2H,4H)‐dione 3 with Vilsmeier–Haack reagent under microwave irradiation yielded the α‐β unsaturated carboxyaldehyde 5 . This novel and clean one‐pot methodology, which is characterized by very short reaction time and easy workup procedure, can be exploited to generate some novel condensed isoquinoline derivatives.     

Interplay of Anion-π+ and π+-π+ Interactions in Novel Pyrido[2,1-a]isoquinolinium-Based AIEgens - Substituent- and Counterion-Dependent Fluorescence Modulation and Applications in Live Cell Mitochondrial Imaging**

Recently, the concept of anion-π⁺ interactions has witnessed unique applications in the field of AIEgen development. In this contribution, we disclose a consolidated study of a library of N-doped ionic AIEgens accessed through silver-mediated cyclization of pyridino-alkynes. A thorough photophysical, computational and crystallographic study has been conducted to rationalize the observed substituent- and counterion-dependent fluorescence properties of these luminogens. We further elucidate the prominent role of anion-π⁺ interactions, π⁺-π⁺ interactions and other non-covalent interactions, in inhibiting the undesired ACQ effect. Finally, we have also demonstrated the application of selected AIEgens for imaging of mitochondria in live cells.