351-36-0Relevant articles and documents
An Environmentally Benign, Catalyst-Free N?C Bond Cleavage/Formation of Primary, Secondary, and Tertiary Unactivated Amides
Kumar, Vishal,Dhawan, Sanjeev,Girase, Pankaj Sanjay,Singh, Parvesh,Karpoormath, Rajshekhar
, p. 5627 - 5639 (2021/11/11)
Herein, we report an operationally simple, cheap, and catalyst-free method for the transamidation of a diverse range of unactivated amides furnishing the desired products in excellent yields. This protocol is environmentally friendly and operates under extremely mild conditions without using any promoter or additives. Significantly, this strategy has been implied in the chemoselective synthesis of a pharmaceutical molecule, paracetamol, on a gram-scale with excellent yield. We anticipate that this universally applicable strategy will be of great interest in drug discovery, biochemistry, and organic synthesis.
Direct para-Selective C-H Amination of Iodobenzenes: Highly Efficient Approach for the Synthesis of Diarylamines
Chen, Yujie,Huang, Zhibin,Jiang, Yaqiqi,Shu, Sai,Yang, Shan,Shi, Da-Qing,Zhao, Yingsheng
, p. 8226 - 8235 (2021/06/28)
Iodine(III)-mediated synthesis of 4-iodo-N-phenylaniline from iodobenzene has been achieved, and the reaction can proceed under mild conditions. A variety of functional groups were well tolerated, providing the corresponding products in moderate to good yields. The remaining iodine group provides an effective platform for converting the products into several valuable asymmetric diphenylamines. Most importantly, this reaction can be easily scaled up to the ten-gram scale, highlighting its synthetic utility. The mechanistic study revealed that the in situ generated aryl hypervalent iodine intermediate is the key factor to realize this para-selective C-H amination reaction.
Catalyst-free, direct electrochemical synthesis of annulated medium-sized lactams through C-C bond cleavage
Ackermann, Lutz,Huang, Zhixing,Kuniyil, Rositha,Li, Yueheng,Ruan, Zhixiong,Xu, Zhongnan,Zhang, Chao
supporting information, p. 1099 - 1104 (2020/03/11)
A catalyst-free, direct electrochemical synthesis of synthetically challenging medium-sized lactams through C-C bond cleavage has been developed. In contrast to previous typical amidyl radical cyclization, this electrosynthetic approach enabled step-economical ring expansion through a unique remote amidyl migration under mild, metal- and external-oxidant-free conditions in a simple undivided cell. The strategy features unparalleled broad substrate scope with all ring sizes of (hetero)aryl-fused 8-11-membered rings and hetero atom-tethered rings, high yields, and good functional group tolerance. Our experimental and computational findings provided strong support for a SET-based reaction manifold.
Selective C-F Functionalization of Unactivated Trifluoromethylarenes
Vogt, David B.,Seath, Ciaran P.,Wang, Hengbin,Jui, Nathan T.
supporting information, p. 13203 - 13211 (2019/09/03)
Fluorinated organic molecules are pervasive within the pharmaceutical and agrochemical industries due to the range of structural and physicochemical properties that fluorine imparts. Currently, the most abundant methods for the synthesis of the aryl-CF2 functionality have relied on the deoxyfluorination of ketones and aldehydes using expensive and poorly atom economical reagents. Here, we report a general method for the synthesis of aryl-CF2R and aryl-CF2H compounds through activation of the corresponding trifluoromethyl arene precursors. This strategy is enabled by an endergonic electron transfer event that provides access to arene radical anions that lie outside of the catalyst reduction potential. Fragmentation of these reactive intermediates delivers difluorobenzylic radicals that can be intercepted by abundant alkene feedstocks or a hydrogen atom to provide a diverse array of difluoalkylaromatics.
Synthesis of acetamides from aryl amines and acetonitrile by diazotization under metal-free conditions
Duan, Pan,Guo, Yu,Kang, Huan,Li, Yi-Na,Wen, Xianghao,Xiao, Fang,Zeng, Yao-Fu,Zhang, Na-Na
supporting information, p. 2169 - 2172 (2019/11/25)
An efficient and metal-free coupling reaction has been developed that affords acetamides from the corresponding aryl amines and acetonitrile. This method tolerates a wide range of functional groups and is selective toward aryl amines. Preliminary mechanistic studies were conducted.
Regioselective nitration of anilines with Fe(NO3)3·9H2O as a promoter and a nitro source
Gao, Yang,Mao, Yuanyou,Zhang, Biwei,Zhan, Yingying,Huo, Yanping
supporting information, p. 3881 - 3884 (2018/06/08)
An efficient Fe(NO3)3·9H2O promoted ortho-nitration reaction of aniline derivatives has been developed. This reaction may go through a nitrogen dioxide radical (NO2) intermediate, which is generated by the thermal decomposition of iron(iii) nitrate. The practicality of the present method using nontoxic and inexpensive iron reagents has been shown by the broad substrate scope and applications.
Direct Photocatalytic Synthesis of Medium-Sized Lactams by C?C Bond Cleavage
Wang, Na,Gu, Qiang-Shuai,Li, Zhong-Liang,Li, Zhuang,Guo, Yu-Long,Guo, Zhen,Liu, Xin-Yuan
supporting information, p. 14225 - 14229 (2018/10/15)
Reported is a novel two-step ring-expansion strategy for expeditious synthesis of all ring sizes of synthetically challenging (hetero)aryl-fused medium-sized lactams from readily available 5–8-membered cyclic ketones. This step-economic approach features a remote radical (hetero)aryl migration from C to N under visible-light conditions. Broad substrate scope, good functional-group tolerance, high efficiency, and mild reaction conditions make this procedure very attractive. In addition, this method also provides expedient access to 13–15-membered macrolactams upon an additional one-step manipulation. Mechanistic studies indicate that the reaction involves an amidyl radical and is promoted by acid.
Monoprotected l-Amino Acid (l-MPAA), Accelerated Bromination, Chlorination, and Iodination of C(sp2)?H Bonds by Iridium(III) Catalysis
Kathiravan, Subban,Nicholls, Ian A.
supporting information, p. 7031 - 7036 (2017/05/29)
Halogenated arenes are important structural motifs commonly found in biologically active molecules and used for a variety of transformations in organic synthesis. Herein, we report the mono-protected l-amino acid (l-MPAA) accelerated iridium(III)-catalyzed halogenation of (hetero)anilides at room temperature. This reaction constitutes the first example of an iridium(III)/l-MPAA-catalyzed general halogenation of (hetero)arenes through C(sp2)?H activation. Furthermore, we demonstrate the potential utility of our method through its use in the synthesis of a quinolone derivative.
Acetanilide and bromoacetyl-lysine derivatives as activators for human histone deacetylase 8
Mukhtar, Yusif M.,Huang, Yajun,Liu, Jiajia,Chen, Di,Zheng, Weiping
supporting information, p. 2319 - 2323 (2017/05/09)
In the current study, seven compounds (i.e. 1–7) were found to be novel activators for the Nε-acetyl-lysine deacetylation reaction catalyzed by human histone deacetylase 8 (HDAC8). When assessed with the commercially available HDAC8 peptide substrate Fluor-de-Lys-HDAC8 that harbors the unnatural 7-amino-4-methylcoumarin (AMC) residue immediately C-terminal to the Nε-acetyl-lysine residue to be deacetylated, our compounds exhibited comparable activation potency to that of TM-2-51, the strongest HDAC8 activator reported in the current literature. However, when assessed with an AMC-less peptide substrate derived from the native HDAC8 non-histone substrate protein Zinc finger protein ZNF318, while our compounds were all found to be able to activate HDAC8 deacetylation reaction, TM-2-51 was found not to be able to. Our compounds also seemed to be largely selective for HDAC8 over other classical HDACs. Moreover, treatment with the strongest activator among our compounds (i.e. 7) was found to decrease the KM of the above AMC-less HDAC8 substrate, while nearly maintaining the kcat of the HDAC8-catalyzed deacetylation on this substrate.
2-bromo-5- fluorine three fluorine methylbenzene preparation method
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Paragraph 0093-0097, (2017/04/03)
The invention discloses a method for preparing 2-bromine-5-trifluorotoluene chloride. The method comprises the following step: under an anhydrous condition and in an organic solvent, performing cracking reaction on an anhydrous compound 1 or a compound 1', thereby preparing 2-bromine-5-trifluorotoluene chloride. According to the method, the reaction of an upper amino protecting group of m-trifluoromethyl phenylamine, the bromination reaction and the reaction of removing the amino protecting group can be all performed in one same reaction kettle without transferring or storing materials. The raw materials used in the method disclosed by the invention are cheap and easy to obtain, the reaction step is short, the reaction condition is gentle, the utilization rate of bromine is high, and the positioning selectivity of bromine feeding is high, so that a final product is low in isomeride impurity, high in reaction conversion rate, high in yield, high in product purity, low in production cost is low and applicable to industrialization production. The compound 1 and compound 1' are as shown in the specification.
