67428-04-0Relevant articles and documents
Selective carbene transfer to amines and olefins catalyzed by ruthenium phthalocyanine complexes with donor substituents
Cailler, Lucie P.,Kroitor, Andrey P.,Martynov, Alexander G.,Gorbunova, Yulia G.,Sorokin, Alexander B.
supporting information, p. 2023 - 2031 (2021/02/26)
Electron-rich ruthenium phthalocyanine complexes were evaluated in carbene transfer reactions from ethyl diazoacetate (EDA) to aromatic and aliphatic olefins as well as to a wide range of aromatic, heterocyclic and aliphatic amines for the first time. It was revealed that the ruthenium octabutoxyphthalocyanine carbonyl complex [(BuO)8Pc]Ru(CO) is the most efficient catalyst converting electron-rich and electron-poor aromatic olefins to cyclopropane derivatives with high yields (typically 80-100%) and high TON (up to 1000) under low catalyst loading and nearly equimolar substrate/EDA ratio. This catalyst shows a rare efficiency in the carbene insertion into amine N-H bonds. Using a 0.05 mol% catalyst loading, a high amine concentration (1 M) and 1.1 eq. of EDA, a number of structurally divergent amines were selectively converted to mono-substituted glycine derivatives with up to quantitative yields and turnover numbers reaching 2000. High selectivity, large substrate scope, low catalyst loading and practical reaction conditions place [(BuO)8Pc]Ru(CO) among the most efficient catalysts for the carbene insertion into amines.
Bromomethyl Silicate: A Robust Methylene Transfer Reagent for Radical-Polar Crossover Cyclopropanation of Alkenes
Luo, Wenping,Fang, Yewen,Zhang, Li,Xu, Tianhang,Liu, Yongjun,Li, Yan,Jin, Xiaoping,Bao, Jiakan,Wu, Xiaodong,Zhang, Zongyong
supporting information, p. 1778 - 1781 (2020/03/11)
A general protocol for visible-light-induced cyclopropanation of alkenes was developed with bromomethyl silicate as a methylene transfer reagent, offering a robust tool for accessing highly valuable cyclopropanes. In addition to α-aryl or methyl-substituted Michael acceptors and styrene derivatives, the unactivated 1,1-dialkyl ethylenes were also shown to be viable substrates. Apart from realizing the cyclopropanation of terminal alkenes, the methyl transfer reaction has been further demonstrated to be amenable to the internal olefins. The photocatalytic cyclopropanation of 1,3-bis(1-arylethenyl)benzenes was also achieved, giving polycyclopropane derivatives in excellent yields. With late-stage cyclopropanation as the key strategy, the synthetic utility of this transformation was also demonstrated by the total synthesis of LG100268.
Comparative Study of the Electronic Structures of μ-Oxo, μ-Nitrido, and μ-Carbido Diiron Octapropylporphyrazine Complexes and Their Catalytic Activity in Cyclopropanation of Olefins
Cailler, Lucie P.,Clémancey, Martin,Barilone, Jessica,Maldivi, Pascale,Latour, Jean-Marc,Sorokin, Alexander B.
, p. 1104 - 1116 (2020/02/04)
The electronic structure of three single-Atom bridged diiron octapropylporphyrazine complexes (FePzPr8)2X having Fe(III)-O-Fe(III), Fe(III)-N-Fe(IV) and Fe(IV)-C-Fe(IV) structural units was investigated by M?ssbauer spectroscopy and density functional theory (DFT) calculations. In this series, the isomer shift values decrease, whereas the values of quadrupole splitting become progressively greater indicating the increase of covalency of Fe-X bond in the μ-oxo, μ-nitrido, μ-carbido row. The M?ssbauer data point to low-spin systems for the three complexes, and calculated data with B3LYP-D3 show a singlet state for μ-oxo and μ-carbido and a doublet state for μ-nitrido complexes. An excellent agreement was obtained between B3LYP-D3 optimized geometries and X-ray structural data. Among (FePzPr8)2X complexes, μ-oxo diiron species showed a higher reactivity in the cyclopropanation of styrene by ethyl diazoacetate to afford a 95% product yield with 0.1 mol % catalyst loading. A detailed DFT study allowed to get insight into electronic structure of binuclear carbene species and to confirm their involvement into carbene transfer reactions.
Iron/N-doped graphene nano-structured catalysts for general cyclopropanation of olefins
Bartling, Stephan,Beller, Matthias,Ferretti, Francesco,Formenti, Dario,Junge, Kathrin,Kreyenschulte, Carsten,Ragaini, Fabio,Sarkar, Abhijnan
, p. 6217 - 6221 (2020/08/24)
The first examples of heterogeneous Fe-catalysed cyclopropanation reactions are presented. Pyrolysis of in situ-generated iron/phenanthroline complexes in the presence of a carbonaceous material leads to specific supported nanosized iron particles, which are effective catalysts for carbene transfer reactions. Using olefins as substrates, cyclopropanes are obtained in high yields and moderate diastereoselectivities. The developed protocol is scalable and the activity of the recycled catalyst after deactivation can be effectively restored using an oxidative reactivation protocol under mild conditions. This journal is
Synthesis of non-nucleoside anti-viral cyclopropylcarboxacyl hydrazones and initial anti-HSV-1 structure-activity relationship studies
Babu Dokuburra, Chanti,D'Aiuto, Leonardo,Demers, Matthew,McClain, Lora,McNulty, James,Nimgaonkar, Vishwajit L.,Piazza, Paolo,Williamson, Kelly,Zheng, Wenxiao
supporting information, (2020/10/02)
The synthesis of a lead anti-viral cyclopropyl carboxy acyl hydrazone 4F17 (5) and three sequential arrays of structural analogues along with the initial assessment and optimization of the antiviral pharmacophore against the herpes simplex virus type 1 (HSV-1) are reported.
Tuning Rh(ii)-catalysed cyclopropanation with tethered thioether ligands
Abshire, Anthony,Cressy, Derek,Darko, Ampofo,Sheffield, William,Zavala, Cristian
supporting information, p. 15779 - 15787 (2020/11/24)
Dirhodium(ii) paddlewheel complexes have high utility in diazo-mediated cyclopropanation reactions and ethyl diazoacetate is one of the most commonly used diazo compounds in this reaction. In this study, we report our efforts to use tethered thioether ligands to tune the reactivity of RhII-carbene mediated cyclopropanation of olefins with ethyl diazoacetate. Microwave methods enabled the synthesis of a family of RhII complexes in which tethered thioether moieties were coordinated to axial sites of the complex. Different tether lengths and thioether substituents were screened to optimise cyclopropane yields and minimise side product formation. Furthermore, good yields were obtained when equimolar diazo and olefin were used. Structural and spectroscopic investigation revealed that tethered thioethers changed the electronic structure of the rhodium core, which was instrumental in the performance of the catalysts. Computational modelling of the catalysts provided further support that the tethered thioethers were responsible for increased yields. This journal is
Z-bpy, a New C2-Symmetric Bipyridine Ligand and Its Application in Enantioselective Copper(I)-Catalyzed Cyclopropanation of Olefins
Ouyang, Yizhao,Zhan, Miao,Zhou, Jing,Jiao, Jiao,Hu, Hao,Yamada, Yoichi M. A.,Li, Pengfei
supporting information, p. 807 - 810 (2019/07/04)
A rigid C2-symmetric chiral bipyridine ligand Z-bpy with a triptycene-like backbone was designed and synthesized from simple chemicals in a scalable route. Using this new ligand, copper(I) catalyzed cyclopropanation of styrenes with commercial ethyl diazoacetate produced various corresponding cyclopropanes in high yields, diastereoselectivity and enantioselectivity up to 97% ee.
Chiral 2,2'-dipyridine ligand, preparation method thereof, and application of ligand in preparation of chiral cyclopropane derivatives
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Paragraph 0127; 0128; 0129, (2019/10/01)
The invention provides a chiral 2,2'-dipyridine ligand, a preparation method thereof, and an application of the ligand in the preparation of chiral cyclopropane derivatives. The chiral 2,2'-dipyridineligand is represented by formula (1) or formula (1'), can be used for efficiently preparing the chiral cyclopropane derivatives, and has the advantages of high yield, good stereoselectivity, easinessin separation and purification, and high practical values.
2,2-diphenylcyclopropyl compound and synthesis method thereof
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, (2019/10/01)
The present invention provides a 2,2-diphenylcyclopropyl compound, which has a chemical name 2,2-diphenyl methyl cyclopropanecarboxylate compound, wherein the structure formula is defined in the specification, and the group R in the structure formula represents C1-C4 short-chain alkane, cycloalkane, halogenated alkane or halogenated cycloalkane. The present invention further provides a synthesis method of the 2,2-diphenylcyclopropyl compound, wherein the system method comprises: synthesizing Benzophenone hydrazone, synthesizing diphenyldiazomethane, and synthesizing the target product. According to the present invention, the three-membered ring of the 2,2-diphenyl methyl cyclopropanecarboxylate compound contains a chiral center, which can be used as a chiral precursor to introduce the chiral carbon atom into the reaction product so as to provide more possibility for the development of active compounds; and the synthesis method is simple, easy to operate, and suitable for industrial production.
Unexpected formation of a μ-carbido diruthenium(IV) complex during the metalation of phthalocyanine with Ru3(CO)12 and its catalytic actIVity in carbene transfer reactions
Kroitor, Andrey P.,Cailler, Lucie P.,Martynov, Alexander G.,Gorbunova, Yulia G.,Tsivadze, Aslan Yu.,Sorokin, Alexander B.
supporting information, p. 15651 - 15655 (2017/12/02)
A μ-carbido diruthenium(iv) phthalocyanine complex was prepared for the first time from the free-base octabutoxyphthalocyanine by direct metalation with Ru3(CO)12. The first examples of the catalytic activity of Ru(iv) binuclear phthalocyanines were demonstrated by the cyclopropanation of aromatic olefins and carbene insertion into the N-H bonds of aromatic or aliphatic amines with turnover numbers of 680-1000 and 580-1000, respectively.
