66715-65-9Relevant academic research and scientific papers
Development of a robust ring-closing metathesis reaction in the synthesis of SB-462795, a cathepsin K inhibitor
Wang, Huan,Goodman, Steven N.,Dai, Qunying,Stockdale, Gregory W.,Clark Jr., William M.
, p. 226 - 234 (2008)
The development of a robust and high-yielding ring-closing metathesis (RCM) reaction and its demonstration on multikilogram scale are described. A detailed understanding of the impact of impurities on the RCM reaction was achieved using a variety of chemical and statistical methods. Specifically, individual impurities were evaluated in spiking studies to identify those that negatively affected the RCM reaction. Projection methods (PCA and PLS) were applied to historical data to identify the main sources of variation in starting material quality and determine the main detrimental impurities that impeded the RCM reaction. The synthesis of the starting material was then modified to adequately control these key impurities, which in turn ensured a robust RCM process. Finally, the robustness of the RCM reaction was assessed using a probability-based approach.
Synthetically tunable iridium(III) bis-pyridine-2-sulfonamide complexes as efficient and durable water oxidation catalysts
Li, Mo,Bernhard, Stefan
, p. 19 - 27 (2017)
A series of phenylene-linked iridium bis-pyridine-2-sulfonamide (bpsa) complexes substituted with electron-donating and electron-withdrawing groups and a new bpsa complex containing naphthalene linkage were synthesized and investigated as efficient and robust water oxidation catalysts. It was found that the oxidation potentials of these substituted complexes are within a broad range, which reflects their effectively tuned electronic structures. Under various water oxidation conditions, diverse kinetics behaviors are observed. The reaction mechanism strongly depends on the structure of the catalyst, and the nature of the oxidant as well as their ratios and concentrations. As evidenced by cyclic voltammetry and DFT calculations, the addition of electron-donating substituents greatly destabilizes the HOMO of the catalyst and thus facilitates the initial oxidation process. On the other hand, the limited driving force provided by the oxidized state of an electron-rich catalyst also impedes efficient water oxidation reactions. The robustness of a water oxidation catalyst is critical, and long-term reactions have exhibited turnover numbers (TONs) of up to 16,200.
NaClO2-mediated preparation of pyridine-2-sulfonyl chlorides and synthesis of chiral sulfonamides
Xu, Dong,Yang, Shiyi,Gao, Aijun,Yang, Zhanhui
, p. 463 - 473 (2020/07/03)
A simple method to prepare azaarenesulfonyl chlorides by NaClO2-mediated oxidative chlorination of azaarenethiols have been developed, with water as the solvent. Easy purification by simple extraction and concentration gives the products in good yields. The azaarenesulfonyl chlorides readily undergo condensation with chiral amines to afford chiral sulfonamides.
Nickel-Catalyzed Intramolecular Desulfitative C - N Coupling: A Synthesis of Aromatic Amines
Chen, Xuemeng,Jia, Xiuwen,Kramer, S?ren,Li, Yue,Lian, Zhong,Liu, Jiangjun,Sun, Haotian
, p. 5702 - 5711 (2020/05/19)
A nickel-catalyzed intramolecular C - N coupling reaction via SO2 extrusion is presented. The use of a catalytic amount of BPh3 allows the transformation to take place under much milder conditions (60 °C) than previously reported C - N coupling reactions by CO or CO2 extrusion (160-180 °C). In addition, this method displays good functional group tolerance and versatility, as it can be applied to the synthesis of dialkyl aryl amines, alkyl diaryl amines, and triaryl amines. The robustness of the desulfitative C - N coupling is demonstrated by three high-yielding gram-scale reactions.
Cyanide-Free Synthesis of Air Stable N-Substituted Li and K Cyanamide Salts from Tetrazoles. Applications toward the Synthesis of Primary and Secondary Cyanamides as Precursors to Amidines
Duchamp, Edouard,Hanessian, Stephen
supporting information, p. 8487 - 8491 (2020/11/12)
A practical two-step synthesis of N,N′-disubstituted cyanamides consists in the low-temperature metalation of N-substituted 5H-tetrazoles that undergo spontaneous cycloreversion at 0 °C releasing dinitrogen, and forming N-metalated cyanamides that can be reacted in situ with a variety of electrophiles. Remarkably, the N-substituted Li and K cyanamides are air stable white solids at room temperature. Addition of lithium organometallics to the N,N′-disubstituted cyanamides provides a new method for accessing N,N′-disubstituted amidines.
Access to Benzazepinones by Pd-Catalyzed Remote C-H Carbonylation of γ-Arylpropylamine Derivatives
Martínez-Mingo, Mario,Rodríguez, Nuria,Gómez Arrayás, Ramón,Carretero, Juan C.
supporting information, p. 4345 - 4349 (2019/06/14)
A general method for the construction of seven-membered rings through Pd-catalyzed C(sp2)-H carbonylation at the remote ?-position of γ-arylpropylamine derivatives, including chiral α-amino acids, has been developed using Mo(CO)6 as the CO source, furnishing richly functionalized benzo[c]azepin-1-one derivatives. The readily removable N-SO2Py protecting/directing group provides high levels of chemo-, regio- and diastereoselectivity. Furthermore, this method is amenable to the postsynthetic modification of complex molecules such as small peptides.
Transition-Metal-Catalyzed Transformation of Sulfonates via S-O Bond Cleavage: Synthesis of Alkyl Aryl Ether and Diaryl Ether
Chen, Xuemeng,Xiao, Xue,Sun, Haotian,Li, Yue,Cao, Haolin,Zhang, Xuemei,Yang, Shengyong,Lian, Zhong
supporting information, p. 8879 - 8883 (2019/11/14)
The catalytic conversion of sulfonates, a versatile class of pharmaceutical intermediates, is usually based on C-O bond cleavage. In this paper, however, we discover a rare transformation of sulfonates via S-O bond cleavage catalyzed by transition metal, through which alkyl sulfonates could undergo an intramolecular desulfitative C-O coupling to form aryl alkyl ethers in the presence of a nickel catalyst. Meanwhile, aryl sulfonates perform similarly to give diaryl ethers catalyzed by a palladium complex. This transformation could tolerate a wide range of functionalities. Controlled experiments reveal that the 2-pyridyl group is necessary to promote the reaction as designed. Crossover experiments proved that this transformation might proceed partly in an intermolecular pathway.
Transition-Metal-Free Amination of Pyridine-2-sulfonyl Chloride and Related N-Heterocycles Using Magnesium Amides
Balkenhohl, Moritz,Fran?ois, Cyril,Sustac Roman, Daniela,Quinio, Pauline,Knochel, Paul
supporting information, p. 536 - 539 (2017/02/10)
A new transition-metal-free amination of pyridine-2-sulfonyl chloride and related N-heterocycles using magnesium amides of type R2NMgCl·LiCl is reported. Additionally, the directed ortho-magnesiation of pyridine-2-sulfonamides using TMPMgCl·LiCl was investigated. Reaction of the magnesium intermediates with various electrophiles and subsequent amination using magnesium amides led to a range of 2,3-functionalized pyridines. Also, cyclization reactions providing an aza-indole and an aza-carbazole were carried out.
Palladium-Catalyzed C?H Functionalization of Phenyl 2-Pyridylsulfonates
Li, Bin,Guo, Dong-Dong,Guo, Shi-Huan,Pan, Gao-Fei,Gao, Ya-Ru,Wang, Yong-Qiang
, p. 130 - 144 (2017/01/06)
An efficient palladium(II)-catalyzed intermolecular direct ortho-alkenylation and acetoxylation of phenols has been developed. The reaction proceeded via a seven-membered cyclopalladated intermediate and showed complete regio- and diastereoselectivity. The approach also provided an efficient route for the synthesis of coumarins and benzofurans.
Aminoxidation of Arenethiols to N-Chloro-N-sulfonyl Sulfinamides
Yang, Zhanhui,Xu, Wei,Wu, Qiuyue,Xu, Jiaxi
, p. 3051 - 3057 (2016/04/26)
A simple and efficient method to synthesize N-chloro-N-sulfonylsulfinamides by the direct aminoxidation of arenethiols under aqueous and mild conditions is disclosed, geminally installing the oxo and amino groups on the sulfur atom of arenethiols. The products have been primarily developed as sulfinylation reagents to convert Grignard reagents into sulfoxides, and as amination reagents to convert secondary amines into hydrazine derivatives.
