6092-71-3Relevant academic research and scientific papers
α-Nitrosostyrenes as Three-Atom Units for the (3+1) Cyclization Reaction: Facile Access to 2,3-Dihydrodiazete N-Oxides and Their Diversified Synthetic Conversions
Shen, Li-Wen,Wang, Zhen-Hua,You, Yong,Yuan, Wei-Cheng,Zhao, Jian-Qiang,Zhou, Ming-Qiang
supporting information, p. 1094 - 1099 (2022/02/10)
An unprecedented (3+1) cyclization of α-nitrosostyrenes, generated in situ from α-bromooximes, and N-tosyloxycarbamates was developed, which enables the synthesis of a range of structurally unique and hitherto unexplored 2,3-dihydrodiazete N-oxides in mod
Intramolecular C(sp3)–H Bond Oxygenation by Transition-Metal Acylnitrenoids
Chen, Shuming,Hong, Yubiao,Houk, K. N.,Ivlev, Sergei,Meggers, Eric,Tan, Yuqi,Zhou, Zijun
supporting information, p. 21706 - 21710 (2020/10/02)
This study demonstrates for the first time that easily accessible transition-metal acylnitrenoids can be used for controlled direct C(sp3)-H oxygenations. Specifically, a ruthenium catalyst activates N-benzoyloxycarbamates as nitrene precursors towards regioselective intramolecular C?H oxygenations to provide cyclic carbonates, hydroxylated carbamates, or 1,2-diols. The method can be applied to the chemoselective C?H oxygenation of benzylic, allylic, and propargylic C(sp3)?H bonds. The reaction can be performed in an enantioselective fashion and switched in a catalyst-controlled fashion between C?H oxygenation and C?H amination. This work provides a new reaction mode for the regiocontrolled and stereocontrolled conversion of C(sp3)-H into C(sp3)?O bonds.
Photocatalytic Intramolecular C-H Amination Using N-Oxyureas as Nitrene Precursors
Ivanovich, Ryan A.,Polat, Dilan E.,Beauchemin, André M.
supporting information, p. 6360 - 6364 (2020/09/02)
Nitrenes are remarkable high-energy chemical species that enable direct C-N bond formation, typically via controlled reactions of metal-stabilized nitrenes. Here, in contrast, the combined use of photocatalysis with careful engineering of the precursor enabled C-H amination forming imidazolidinones and related nitrogen heterocycles from readily accessible hydroxylamine precursors. Preliminary mechanistic results are consistent with the formation of free carbamoyl triplet nitrenes as reactive intermediates.
Synthesis of Sulfinamidines and Sulfinimidate Esters by Transfer of Nitrogen to Sulfenamides
Andresini, Michael,Spennacchio, Mauro,Romanazzi, Giuseppe,Ciriaco, Fulvio,Clarkson, Guy,Degennaro, Leonardo,Luisi, Renzo
supporting information, p. 7129 - 7134 (2020/10/02)
In this work we report a new synthetic tactic for the straightforward preparation of hardly accessible sulfinamidines and sulfinamide esters, by using a simple metal-free protocol. The process is robust and uses readily available sulfenamides as the S-don
Regioselective Synthesis of 2-Vinylanilines Using O-aroyloxycarba-mates by Sequential Decarboxylation/Amination/Heck Reaction
Li, Peihe,Ma, Nuannuan,Li, Jikun,Wang, Zheng,Dai, Qipu,Hu, Changwen
, p. 8251 - 8257 (2017/08/14)
A new sequential approach for 2-vinylanilines utilizing aryl carboxylic acids as stable, inexpensive and widely available arylating reagents is described. Employing a Pd-POVs catalyst system, this protocol is not only overcoming the restriction barrier of decarboxylative coupling to ortho-substituted substrates, but also provides site-special to create new C(sp2)-N and C(sp2)-C(sp2) bonds. Mechanistic experiments suggest the cleavage of C(sp2)-COOH gives priority to C(sp2)-X bond in this reaction.
Palladium-Catalyzed Decarboxylative Synthesis of Arylamines
Dai, Qipu,Li, Peihe,Ma, Nuannuan,Hu, Changwen
supporting information, p. 5560 - 5563 (2016/11/17)
A novel approach has been developed for the synthesis of arylamines via the palladium-catalyzed intramolecular decarboxylative coupling (IDC) of aroyloxycarbamates, obtained in situ by reacting aryl carboxylic acids with hydroxycarbamates. The reaction offers facile access to structurally diverse arylamines with the site-specific formation of the C(sp2)-N bond under mild conditions.
N-tosyloxycarbamates as a source of metal nitrenes: Rhodium-catalyzed C-H insertion and aziridination reactions
Lebel, Helene,Huard, Kim,Lectard, Sylvain
, p. 14198 - 14199 (2007/10/03)
The rhodium-catalyzed decomposition of N-tosyloxycarbamates to generate metal nitrenes which undergo intramolecular C-H insertion or aziridination reaction is described. Aliphatic N-tosyloxycarbamates produce oxazolidinones with high yields and stereospecificity through insertion in benzylic, tertiary, and secondary C-H bonds. Intramolecular aziridination occurs with allylic N-tosyloxycarbamates to produce aziridines as single diastereomers. The reaction proceeds at room temperature using a rhodium catalyst and an excess of potassium carbonate and does not require the use of strong oxidant, such as hypervalent iodine reagents. A rhodium nitrene species is presumably involved, as both reactions are stereospecific. Copyright
