879767-00-7Relevant academic research and scientific papers
Rhodium(III) Dihalido Complexes: The Effect of Ligand Substitution and Halido Coordination on Increasing Cancer Cell Potency
Lord, Rianne M.,Zegke, Markus,Basri, Aida M.,Pask, Christopher M.,McGowan, Patrick C.
, p. 2076 - 2086 (2021)
This work presents the synthesis of eight new rhodium(III) dihalido complexes, [RhX2(L)(LH)] (where X = Cl or I), which incorporate two bidentate N-(3-halidophenyl)picolinamide ligands. The ligands have different binding modes in the complexes, whereby one is neutral and bound via N,N (LH) coordination, while the other is anionic and bound via N,O (L) coordination. The solid state and solution studies confirm multiple isomers are present when X = Cl; however, after a halide exchange with potassium iodide (X = I) the complexes exist exclusively as single stable trans isomers. NMR studies reveal the Rh(III) trans diiodido complexes remain stable in aqueous solution with no ligand exchange reported over 96 h. Chemosensitivity data against a range of cancer cell lines show two cytotoxic complexes, where L = N-(3-bromophenyl)picolinamide ligand. The results have been compared to the analogous Ru(III) complexes and overall highlight the Rh(III) trans diiodido complex to be ～78× more cytotoxic than the analogous Rh(III) dichlorido complex, unlike the Ru(III) complexes which are equitoxic against all cell lines. Additionally, the Rh(III) trans diiodido complex is more selective toward cancerous cells, with selectivity index (SI) values >25-fold higher than cisplatin against colorectal carcinoma.
A metal-free picolinamide assisted electrochemical ortho-trifluoromethylation of arylamines
Wang, Kai,Hou, Jiahao,Wei, Tingting,Zhang, Changjun,Bai, Renren,Xie, Yuanyuan
supporting information, (2020/12/21)
An eco-friendly and effective electrochemical process was developed for the ortho-trifluoromethylation of arylamines using CF3SO2Na as the trifluoromethyl source, affording the desired products in moderate to good yields with high regioselectivity under mild reaction conditions. Importantly, the requirement for both transition metals and oxidants utilized in previous methods were avoided. A radical mechanism was proposed on the basis of various control experiments.
Copper(ii) mediatedorthoC-H alkoxylation of aromatic amines using organic peroxides: efficient synthesis of hindered ethers
Ghosh, Subhash Chandra,Sahoo, Tapan,Sarkar, Souvik,Sen, Chiranjit
supporting information, p. 8949 - 8952 (2021/09/10)
Synthesis of hindered alkyl aryl ether derivatives (R-O-Ar) remains a huge challenge and highly desirable in organic and medicinal chemistry because extensive substitution on the ether bond prevents the undesired metabolic process and thus avoids rapid de
Copper-Catalyzed Electrophilic Ortho C(sp2)-H Amination of Aryl Amines: Dramatic Reactivity of Bicyclic System
Begam, Hasina Mamataj,Choudhury, Rajarshee,Behera, Ashok,Jana, Ranjan
supporting information, p. 4651 - 4656 (2019/06/17)
A practical copper-catalyzed, 2-picolinamide-directed ortho C-H amination of anilines with benzoyl-protected hydroxylamines has been disclosed that proceeds smoothly without any external stoichiometric oxidant or additives. Remarkably, besides anilines, b
Iron-catalyzed: Ortho trifluoromethylation of anilines via picolinamide assisted photoinduced C-H functionalization
Xia, Chengcai,Wang, Kai,Wang, Guodong,Duan, Guiyun
supporting information, p. 2214 - 2218 (2018/04/05)
A convenient, oxidant-free protocol was developed for the ortho trifluoromethylation of aniline via picolinamide assisted Fe-promoted C-H functionalization under ultraviolet irradiation. In this transformation acetone essentially acted as both a solvent to dissolve reactants and a low-cost radical initiator to efficiently generate a CF3 radical from Langlois' reagent. A broad substrate scope was tolerated and picolinamide bearing strong electron withdrawing groups also could be transformed into the corresponding products with acceptable yields. Furthermore, the value of this method has been highlighted via the efficient synthesis of the nonsteroidal anti-inflammatory drug floctafenine.
Bis-picolinamide Ruthenium(III) Dihalide Complexes: Dichloride-to-Diiodide Exchange Generates Single trans Isomers with High Potency and Cancer Cell Selectivity
Basri, Aida M.,Lord, Rianne M.,Allison, Simon J.,Rodríguez-Bárzano, Andrea,Lucas, Stephanie J.,Janeway, Felix D.,Shepherd, Helena J.,Pask, Christopher M.,Phillips, Roger M.,McGowan, Patrick C.
, p. 6341 - 6356 (2017/05/12)
A library of new bis-picolinamide ruthenium(III) dihalide complexes of the type [RuX2L2] (X=Cl or I, L=picolinamide) have been synthesised and characterised. The complexes exhibit different picolinamide ligand binding modes, whereby one ligand is bound (N,N) and the other bound (N,O). Structural studies revealed a mixture of cis and trans isomers for the [RuCl2L2] complexes but upon a halide exchange reaction to yield [RuI2L2], only single trans isomers were detected. High cytotoxic activity against human cancer cell lines was observed, with the potencies of some complexes similar to or better than cisplatin. The conversion to [RuI2L2] substantially increased the activity towards cancer cell lines by more than twelvefold. The [RuI2L2] complexes displayed potent activity against the A2780cis (cisplatin-resistant human ovarian cancer) cell line, with a more than fourfold higher potency than cisplatin. Equitoxic activity was observed against normoxic and hypoxic cancer cells, which indicates the potential to eradicate both the hypoxic and aerobic fractions of solid tumours with similar efficiency. The activity of selected complexes against non-cancer ARPE-19 cells was also tested. The [RuI2L2] complexes were found to be more potent than the [RuCl2L2] analogues and also more selective towards cancer cells with a selectivity factor in excess of sevenfold.
Copper-catalyzed carboxamide-directed ortho amination of anilines with alkylamines at room temperature
Li, Qiong,Zhang, Shu-Yu,He, Gang,Ai, Zhaoyan,Nack, William A.,Chen, Gong
supporting information, p. 1764 - 1767 (2014/04/17)
In this report, a highly efficient method for the room temperature installation of alkyl amino motifs onto the ortho position of anilines via Cu-catalyzed carboxamide-directed amination with alkylamines is described. This method offers a practical solution for the rapid synthesis of complex arylamines from simple starting materials and enables new planning strategies for the construction of arylamine-containing pharmacophores. A single electron transfer (SET)-mediated mechanism is proposed.
