Article
Chemistry, Physical
Victoria Dimakos, Daniel P. Canterbury, Sebastien Monfette, Philipp C. Roosen, Stephen G. Newman
Summary: This study describes a Pd-catalyzed method for the direct and selective alpha-arylation of cyclic enones using (hetero)aryl triflates. Optimized ligands and additives were employed to achieve high selectivity. Preliminary mechanistic investigations suggest that the reaction proceeds through enone activation and Pd-catalyzed enolate arylation, resembling a Morita-Baylis-Hillman reaction.
Article
Chemistry, Multidisciplinary
Elavarasan Pavithra, Sathananthan Kannadasan, Ponnusamy Shanmugam
Summary: A catalyst-free and green chemical method was developed for the methylenation of indole and N-methyl-7-aza indoles using aqueous formaldehyde. Under microwave irradiation, high yields of respective N,N'-dimethyl-3,3'-bis-7-azaindolylmethanes were obtained. The subsequent oxidation of the products resulted in N,N'-dimethyl-3,3'-bis-7-azaindolylmethanone derivatives in excellent yield. These derivatives, with halogen substitution at the aryl ring, were used in Suzuki coupling reactions to produce highly functionalized fluorescent biaryl derivatives.
Article
Biochemistry & Molecular Biology
Yi-Lin He, Miao Zhong, Zi-Long Song, Yu-Kai Shen, Lanning Zhao, Jianguo Fang
Summary: This study reports the design and synthesis of a series of Baylis-Hillman adducts, among which a typical adduct showed superior cytotoxicity against HepG2 cells. The selected typical adduct was found to selectively target TrxR in HepG2 cells, leading to the disruption of intracellular redox homeostasis. It also arrested the cell cycle and significantly restrained the metastasis of HepG2 cells. These findings suggest that the selected typical adduct, as well as other Baylis-Hillman skeleton-bearing compounds, hold promise as candidate or ancillary agents for the treatment of various cancers.
BIOORGANIC & MEDICINAL CHEMISTRY
(2023)
Article
Chemistry, Organic
Dianpeng Chen, Jianming Li, Xiuhua Zhang, Gongle Liu, Xin Wang, Yongwei Liu, Xuan Liu, Yingying Shan
Summary: A novel method for the synthesis of fused tetracyclic N-heterocycles is described using palladium-catalyzed cyclization of isocyanides with alkyne-tethered aryl iodides. The reaction involves a unique amino-to-alkyl 1,5-palladium migration/intramolecular C(sp(3))-C(sp(2)) coupling sequence. Isocyanide plays multiple roles in this transformation, serving as a C1 synthon, a C1N1 synthon, and the donor of C(sp(3)) for C(sp(3))-C(sp(2)) coupling, and it represents the only successful example of C(sp(3))-H activation of isocyanide.
Article
Chemistry, Multidisciplinary
Bo-Sheng Zhang, Ying-Hui Yang, Fan Wang, Xue-Ya Gou, Xi-Cun Wang, Yong-Min Liang, Yuke Li, Zheng-Jun Quan
Summary: This paper presents the first case of a reductive coupling reaction using indene as a reducing agent, showing a broad substrate scope and various types of reactions. The formation of an eta(3)-palladium indene intermediate was confirmed through control experiments and density functional theory calculations, while the formation of palladium anion intermediates was excluded.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Organic
Yue Wang, Manman Song, Er-Qing Li, Zheng Duan
Summary: This study presents a new palladium/phosphine cooperative catalytic system for the synthesis of bicyclo[3.1.0]hexene derivatives, highlighting the crucial roles of both Pd and phosphine in the selective intermolecular activation of Morita-Baylis-Hillman carbonates. This strategy opens up a new avenue for efficient and economical metal/Lewis base dual catalytic systems and provides valuable clues on solving the limitations of selective activation.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Parasitology
Ana Carolina Santana Vieira, Mariana da Silva Santos, Anderson Brandao Leite, Amanda Evelyn da Silva, Luiz Henrique Agra Cavalcante-Silva, Gabrielle de Souza Augusto Pereira, Sany Delany Gomes Marques, Barbara Viviana de Oliveira Santos, Alysson Wagner Fernandes Duarte, Aline Cavalcante de Queiroz, Kristerson Reinaldo de Luna-Freire, Magna Suzana Alexandre-Moreira
Summary: Leishmaniasis is a neglected disease with limited treatment options and adverse effects. This study evaluated the antileishmanial activity of several derivatives and found that one derivative (1G) showed activity against both promastigote and amastigote forms with low toxicity to macrophages.
PARASITOLOGY RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Ashish Joshi, Shruti Moorthy, Lilesh Rambhai Chavada, Saurabh Kumar Singh, Ashok Kumar Pandey
Summary: A method for accessing isochroman-1-imines by merging C(sp(2))-H allylation and alkene difunctionalization events using N-aroyl aminoesters, MBH acetates, and NBS under Ru(ii)/Ru(iv) catalysis has been developed. The involvement of allyl transfer (redox) process in C-H allylation rather than olefin insertion was proven through H-1 NMR, ESI-MS, HRMS, control reactions, deuterium labeling experiments, and DFT analysis. Scale-up and synthetic transformations demonstrated the sustainability of this method.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Yinuo Li, Cuiyu Bao, Zhoutong Sun, Wuyuan Zhang, Bo Yuan
Summary: The oxidation of benzylic alcohols coupled with the Morita-Baylis-Hillman (MBH) reactions in biocatalytic compatible conditions was evaluated. One-pot cascades were described and compared, including a chemoenzymatic cascade with galactose oxidase (GOase M3-5) and 1,4-Diazabicyclo [2.2.2] octane (DABCO), a concurrent dual-enzyme cascade with GOase M3-5 and a computationally designed enzyme MBHase (BH32.14), and a whole cell biotransformation with co-expression modules of the two enzymes. The cascades showed high conversions and yields, with some products having high optical purity.
Article
Chemistry, Multidisciplinary
Daigo Hayashi, Tomohiro Tsuda, Ryo Shintani
Summary: A palladium-catalyzed skeletal rearrangement has been developed to synthesize highly fused tetrahydrophenanthrosilole derivatives via bond exchange. The reaction conditions can be tuned to produce different products, fused dihydrodibenzosilepin derivatives.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Xian-Zhou Zheng, Kai Chen, Jun-An Xiao, Jun Li, Sha-Sha Wang, Qing-Lan Zhao, Hao-Yue Xiang, Xiao-Qing Chen, Hua Yang
Summary: In a newly developed palladium-catalysed enantioselective nucleophilic substitution reaction, an unusual temperature-enantioselectivity relationship was observed where higher enantioselectivity was achieved at an abnormally high temperature (140 degrees C) in less than 5 minutes. Experimental and computational studies suggest that temperature-dependent changes in the rate-determining steps may be responsible for the abnormal effect of temperature on stereocontrol in this process.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Multidisciplinary Sciences
Daniel A. Strassfeld, Chia-Yu Chen, Han Seul Park, D. Quang Phan, Jin-Quan Yu
Summary: The functionalization of C-H bonds in organic molecules is a direct approach for chemical synthesis. Recent advances in catalysis have allowed various chemical groups to control and direct C(sp(3))-H activation, but alcohols, a common functionality, have remained difficult to react due to their low affinity for catalysts. This study describes ligands that enable alcohol-directed arylation of C(sp(3))-H bonds through charge balance and hydrogen-bonding interactions, thus enhancing substrate-catalyst affinity and enabling previously unknown reactivity.
Article
Chemistry, Applied
Javed Y. Shaikh, Anindita Bhowmick, Abhijit Chatterjee, Nitin A. Thombare, Ramakrishna G. Bhat
Summary: The palladium (II) catalyzed direct C3-(sp(2))-H alkenylation of five membered heterocyclic aldehydes has been developed using 3-aminobutanoic acid as a catalytic transient directing group. This method allows for highly site-selective C3-alkenylation of heterocyclic aldehydes with various acrylates, featuring exclusive E-selectivity and a broad substrate scope. Additionally, this protocol has proven to be useful in the construction of mechanochromic luminogens.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Niannian Ni, Jiawei Chen, Siyu Ding, Dongping Cheng, Xiaonian Li, Xiaoliang Xu
Summary: The Ru-catalyzed coupling reaction of Morita-Baylis-Hillman (MBH) adducts with tertiary amines and alpha-trimethylsilyl amines under visible light showed different chemical reaction characteristics when compared to MBH adducts with ester groups as withdrawing-electron groups. The universality of substrates has been extended, allowing for the synthesis of structurally complementary acrylonitriles in satisfied yields under mild conditions and providing an opportunity to discover new meaningful bioactive compounds.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Eisuke Sato, Ayaka Yukiue, Koichi Mitsudo, Seiji Suga
Summary: Anodic oxidation was used to achieve the aromatization of 1,2,3,4-tetrahydrocarbazoles. Nitrogen-protected tetrahydrocarbazoles were converted to carbazoles with the use of bromide as a mediator. The presence of AcOH and the inexpensive bromide source LiBr allowed for efficient transformation.
Article
Chemistry, Organic
Geeta Devi Yadav, Pooja Chaudhary, Balaram Pani, Surendra Singh
Summary: Chiral transition metal complexes with privileged ligands are efficient catalysts for various asymmetric organic transformations. Transition metal complexes of C1-symmetric pyrrolidine-based ligands have been widely used in asymmetric organic reactions. However, a comprehensive review article on the transition metal complexes of chiral C1-symmetric pyrrolidine-based ligands derived from (L)-proline has not been published.
TETRAHEDRON LETTERS
(2024)
