Synthesis of trifluoromethylated 2<i>H</i>-azirines through Togni reagent-mediated trifluoromethylation followed by PhIO-mediated azirination

Sun, Jiyun; Zhen, Xiaohua; Ge, Huaibin; Zhang, Guangtao; An, Xuechan; Du, Yunfei

doi:10.3762/bjoc.14.123

Cited by 12 publications

(3 citation statements)

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“…2017 年, 江焕峰课题组 [30] 报道了一种在烯胺酮的三氟甲基化方法(Scheme 15). 该方法使用三氟甲基磺酸钠为三氟甲基源, 以叔丁基过氧化氢(TBHP)为氧化剂, 在 DMF 中, 50 ℃下, 搅拌 12 h, 可以中等产率得到同年, 阳华课题组 [31] 2018 年, 杜云飞课题组 [32] 报道了一种 Togni 试剂介…”

Section: 三氟甲基化unclassified

Progress in the Study of α-Functionalization of Enaminone

Liu¹,

Cuan²,

Li³

et al. 2023

Chinese Journal of Organic Chemistry

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Enaminones are versatile and extremely useful building blocks in organic synthesis with the advantages of easy availability, convenient storage, and distinct reactivity. In particular, such compounds are important precursors in heterocyclic chemistry. Recently, transition-metal-catalyzed or transition-metal-free α-functionalization of enaminones by C-H activation has emerged as a more atom-and step-economical strategy for the construction of functionalized enaminones or various heterocycles, and it has attracted the attention of many organic chemists. This review is divided into five sections based on the varied chemical bonds: C-C bond formation, C-O bond formation, C-N bond formation, C-X bond formation, and C-S/Se bond formation. The recent progress in functionalization of enaminone based on the reaction mechanism, reaction system, the scope of substrates, etc. is systematically reviewed. Keywords enaminone; functionalization; coupling reaction; hypervalent iodine 最初, Greenhill [1] 定义烯胺酮是具有烯胺和羰基共轭结构单元的化合物(NC＝CC＝O). 现在烯胺酮的概念早已扩展到缺电子烯胺类似物(NC＝CEWG), 例如烯胺酯、氰基烯胺和硝基烯胺等 [2] . 由于具有共轭的烯胺键和吸电子官能团, 烯胺酮类化合物结构稳定. 同时由于其反应多样性, 烯胺酮作为一种高度活泼的中间体, 越来越广泛地被应用于有机合成, 特别是含氮杂环化合物的合成. 例如, 烯胺酮既可以通过环加成反应构筑各种各样的含氮杂环化合物 [2] , 也可以通过不对称氢化反应得到手性 β-氨基酸 [3a-3b] (Scheme 1). 由于烯胺酮独特的化学性质以及在有机合成中的广泛用途, 一些课题组对烯胺酮化合物参与的化学反应进行了报道. 例如: Elassar 课题组 [4] 对烯胺酮化合物的合成及其化学性质进行了综述; 李明课题组 [5] 对烯胺酮在杂环化合物合成中的应用进行了综述; Stanovnik 课题组 [6] 对烯胺酮(酯)类化合物在非金属参与条件下合成吡啶的方法进行了综述; 万结平课题组对烯胺酮的交叉氨化多组分反应进行了综述 [7a] 以及烯胺酮通过成环反应构筑取代色酮的反应进行了综述 [7b] . 2022 年, 该课题组综述了通过叔烯胺酮的 C-N 键裂解的杂环多样性合成反应 [7c] 以及在水或水介质中烯胺酮反应的最新进展 [7d] . 夏晓峰课题组 [8] 综述了从烯胺酮出发合成含氮杂环的最

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Section: 三氟甲基化unclassified

Progress in the Study of α-Functionalization of Enaminone

Liu¹,

Cuan²,

Li³

et al. 2023

Chinese Journal of Organic Chemistry

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“…Another study by same group reported the synthesis of trifluoromethylated 2 H ‐azirines. In this one‐pot process, the enamine compound reacts with Togni reagent in the presence of CuI to obtain the intermediate β‐trifluoromethylated enamine, which was converted to trifluoromethyl 2 H ‐azirine in the presence of PhIO (Scheme 69) [92].…”

Section: Oxidative Cyclization Of Enamine Derivativesmentioning

confidence: 99%

Synthesis of various functionalized 2H‐azirines: An updated library

Majee

2021

Journal of Heterocyclic Chem

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In the current extensive review, we pay special attention to the progress in the synthesis of 2H‐azirine. Content is organized by several main approaches for the synthesis of 2H‐azirines such as‐ Neber rearrangement, decomposition of vinyl azides, oxidative cyclization of enamines, ring contraction of isoxazoles or oxazaphospholes, radical addition/cyclization of alkynes, Swern oxidation or elimination reactions of aziridine derivatives, catalytic decomposition of α‐oximino diazo compounds, addition of silyldibromomethyllithium compounds to nitriles, addition of carbenes to nitriles and via azirine‐azirine transformations. Some of these approaches open up access to new 2H‐azirine derivatives and make the already established compounds more convenient. A description of these methods and the progress of using well‐known reactions leading to the aziridine system are presented in this section. This review surveys the progress of various functionalized 2H‐azirine formation reactions from the exploration period to the present.

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“…Among various fluorine containing substituents, the trifluoromethyl group (CF 3 ) is highly valuable for applications in drug discovery, as the incorporation of this substituent often significantly improves the lipophilicity, bioavailability and protein-binding affinity of a molecule and suppresses metabolic detoxification processes to increase the in vivo lifetime of a drug. 5 Therefore, the development of efficient and versatile strategies for introducing the CF 3 moiety into various organic molecules has become one of the hottest topics in advanced organic synthesis in recent years. 6 Among the many methods developed, particularly noteworthy is the vicinal halotrifluoromethylation of alkenes due to its high pot- and step-economy for the introduction of two versatile functional groups ( i.e.…”

Section: Introductionmentioning

confidence: 99%