52267-51-3Relevant articles and documents
Comparative study on post-polymerization modification of C1 poly(benzyl 2-ylidene-acetate) and its C2 analog poly(benzyl acrylate)
Krappitz, Tim,Theato, Patrick
, p. 686 - 691 (2016)
The present study investigates the challenging approach of post-polymerization modification on polymers with a sterically demanding reaction center. Therefore, the general possibility to functionalize polymethylene moieties was investigated. Poly(benzyl 2-ylidene-acetate) was synthesized by polymerization of benzyl 2-diazoacetate utilizing [(L-prolinate)RhI(1,5-dimethyl-1,5-cyclooctadiene)] as a catalyst. Subsequently, the modification of C1 polymerized poly(benzyl 2-ylidene-acetate) with amines was analyzed and the obtained data set was compared with experimental data derived for the C2 analog poly(benzyl acrylate). This is the first study on post-polymerization modification utilizing densely functionalized polymethylenes as starting materials.
Photocatalytic gem-Difluoroolefination Reactions by a Formal C?C Coupling/Defluorination Reaction with Diazoacetates
Li, Fang,Pei, Chao,Koenigs, Rene M.
supporting information, (2021/12/14)
The photolysis of diazoalkanes to conduct singlet carbene transfer reactions of colored diazoalkanes has recently attracted significant interest in organic synthesis. Herein, we describe a photocatalytic approach that allows the access of triplet carbene
Catalytic Ring Expansion of Activated Heteroarenes Enabled by Regioselective Dearomatization
Kim, Jiyoung,Yoo, Eun Jeong
, p. 4256 - 4260 (2021/06/28)
Catalytic ring expansion of activated heteroarenes through 1,4-dearomative addition of diazoacetates was established for the construction of various fused azepines by an elaborate control of the reaction kinetics at each step. The use of a silver catalyst was essential to drive the overall reaction for generating the desired seven-membered azepines. Because of the excellent substrate scope and selectivity, the developed methodology presents an innovative approach for the synthesis of multifused azepines, which are biologically relevant molecules.
N-transfer reagent and method for preparing the same and its application
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Page/Page column 26-29; 59-60; 69-72, (2021/06/25)
Provided are a novel N-transfer reagent and a method for preparing the same and its application. The N-transfer reagent is represented by the following Formula (I): The various novel N-transfer reagents of the present invention can be quickly prepared by employing different nitrobenzene precursors. The N-transfer reagents can directly convert a variety of amino compounds into diazo compounds under mild conditions. Particularly, the N-transfer reagents can facilitate the synthesis of the diazo compounds. The application of synthesizing diazo compounds of the present invention can greatly decrease the difficulty in operation, increase the safety during experiments, reduce the cost of production and the environmental pollution, and enhance the industrial value of diazo compounds.
NovelN-transfer reagent for converting α-amino acid derivatives to α-diazo compounds
Lu, Guan-Han,Huang, Tzu-Chia,Hsueh, Hsiao-Chin,Yang, Shin-Cherng,Cho, Ting-Wei,Chou, Ho-Hsuan
supporting information, p. 4839 - 4842 (2021/05/25)
A novel universalN-transfer reagent for direct and effective transformation of α-amino ketones, acetamides, and esters to the corresponding α-diazo products under mild basic conditions has been developed. This one-step synthetic approach not only allows for generation of α-substituted-α-diazo carbonyl compounds from α-amino acid derivatives but also permits preparation of α-diazo dipeptides fromN-terminal dipeptides (32 examples, up to 91%).
Engineering Dirhodium Artificial Metalloenzymes for Diazo Coupling Cascade Reactions**
Bultman, Max J.,Huang, Rui,Lewis, Jared C.,Li, Ying,Roux, Benoit,Upp, David M.
supporting information, p. 23672 - 23677 (2021/08/23)
Artificial metalloenzymes (ArMs) are commonly used to control the stereoselectivity of catalytic reactions, but controlling chemoselectivity remains challenging. In this study, we engineer a dirhodium ArM to catalyze diazo cross-coupling to form an alkene that, in a one-pot cascade reaction, is reduced to an alkane with high enantioselectivity (typically >99 % ee) by an alkene reductase. The numerous protein and small molecule components required for the cascade reaction had minimal effect on ArM catalysis. Directed evolution of the ArM led to improved yields and E/Z selectivities for a variety of substrates, which translated to cascade reaction yields. MD simulations of ArM variants were used to understand the structural role of the cofactor on ArM conformational dynamics. These results highlight the ability of ArMs to control both catalyst stereoselectivity and chemoselectivity to enable reactions in complex media that would otherwise lead to undesired side reactions.
Cross coupling of sulfonyl radicals with silver-based carbenes: A simple approach to β-carbonyl arylsulfones
Li, Jingjing,Lian, Pengcheng,Wan, Xiaobing,Wang, Hanghang,Zheng, Yonggao
supporting information, p. 2163 - 2169 (2020/03/27)
A coupling reaction between sulfonyl radicals and silver-based carbenes has been well established. This simple radical-carbene coupling (RCC) process provided an efficient approach to a variety of β-carbonyl arylsulfones from sodium arylsulfinates and diazo compounds, and was characterized by wide substrate scope, easy scale-up, simple manipulation, accessible starting materials, and mild reaction conditions.
A General Catalytic Route to Enantioenriched Isoindolinones and Phthalides: Application in the Synthesis of (S)-PD 172938
Ray, Sumit K.,Sadhu, Milon M.,Biswas, Rayhan G.,Unhale, Rajshekhar A.,Singh, Vinod K.
supporting information, (2019/01/21)
Chiral Br?nsted acid catalyzed enantioselective syntheses of isoindolinones and phthalides have been accomplished via tandem Mannich-lactamization and aldol-lactonization reactions, respectively. A variety of enantioenriched isoindolinones (up to 99% ee) and phthalides (up to 85% ee) containing α-diazoesters were afforded in excellent yields. Furthermore, a concise synthesis of (S)-PD 172938 has been demonstrated by using this protocol.
A General Catalytic Route to Enantioenriched Isoindolinones and Phthalides: Application in the Synthesis of (S)-PD 172938
Ray, Sumit K.,Sadhu, Milon M.,Biswas, Rayhan G.,Unhale, Rajshekhar A.,Singh, Vinod K.
supporting information, p. 417 - 422 (2019/01/23)
Chiral Br?nsted acid catalyzed enantioselective syntheses of isoindolinones and phthalides have been accomplished via tandem Mannich-lactamization and aldol-lactonization reactions, respectively. A variety of enantioenriched isoindolinones (up to 99% ee) and phthalides (up to 85% ee) containing α-diazoesters were afforded in excellent yields. Furthermore, a concise synthesis of (S)-PD 172938 has been demonstrated by using this protocol.
Nickel-Catalyzed Transformation of Diazoacetates to Alkyl Radicals Using Alcohol as a Hydrogen Source
Zhao, Jingjing,Li, Pan,Xu, Yaohua,Shi, Yixin,Li, Fuwei
supporting information, p. 9386 - 9390 (2019/11/28)
A nickel-catalyzed transformation of diazoacetates to α-carbonyl methylene radicals has been disclosed in the presence of hyperoxide using ethanol as a hydrogen source and solvent. This strategy is successfully applied in the formation of indolin-2-ones or 1,4-dicarbonyl compounds from acrylamides or enamides in moderate to good yields. These reactions undergo radical addition onto C-C double bonds followed by a cyclization/oxidation or an oxidation/hydrolysis process, respectively.
