5371-52-8Relevant articles and documents
Dioxygen activation by siloxide complexes of chromium(II) and chromium(IV)
Schax, Fabian,Bill, Eckhard,Herwig, Christian,Limberg, Christian
, p. 12741 - 12745 (2014)
The reaction of a tripodal trisilanol with n-butyllithium and CrCl2 results in a dinuclear CrII complex (1), which is capable of cleaving O2 to yield in a unique complex (2) with an asymmetric diamond core composed of two CrIV=O units. Magnetic susceptibility data reveal significant exchange coupling of CrII (S=2) in 1 and large zero-field splitting for CrIV (S=1) in 2 owing to strong spin-orbit coupling of the ground state. The CrIV=O compound can also be generated using PhIO, and evidence was gathered that although it is the stable product isolated after excessive O2 treatment, it further activates O2 to yield an intermediate species that oxidizes THF or Me-THF. By extensive 18O labeling studies we were able to show, that in the course of this process 18O2 exchanges its label with siloxide O atoms of the ligand via terminal oxido ligands.
Synthesis of functionalized bicyclic imines via intramolecular azide-alkene 1,3-dipolar cycloaddition/intramolecular stork alkylation cascade reaction
De Miguel, Irene,Velado, Marina,Herradon, Bernardo,Mann, Enrique
, p. 1237 - 1242 (2013)
A cascade intramolecular azide-alkene 1,3-dipolar cycloaddition/Stork alkylation reaction has been developed for the synthesis of functionalized cyclic imines with a pyrroline and piperideine structures, employing readily available ω-azidodienes. Copyright
Genotoxicity screening for N-nitroso compounds. Electrochemical and electrochemiluminescent detection of human enzyme-generated DNA damage from N-nitrosopyrrolidine
Krishnan, Sadagopan,Hvastkovs, Eli G.,Bajrami, Besnik,Jansson, Ingela,Schenkman, John B.,Rusling, James F.
, p. 1713 - 1715 (2007)
We report for the first time voltammetric/electrochemiluminescent sensors applied to predict genotoxicity of N-nitroso compounds bioactivated by human cytochrome P450 enzymes. The Royal Society of Chemistry.
Free-radical approaches to stemoamide and analogues
Bogliotti, Nicolas,Dalko, Peter I.,Cossy, Janine
, p. 9528 - 9531 (2006)
(Chemical Equation Presented) Two approaches allowing access to the tricyclic stemona backbone are presented. Both approaches rely on a free-radical cyclization reaction as the key step. In the formal synthesis of (±)-stemoamide, the construction of the A ring of the natural product was achieved via a 5-exo-trig radical cyclization with atom transfer. The two diastereoisomers issuing from this cyclization showed different reactivity while forming the seven-membered ring of the final product. In the second part of this study, a 1-exo-trig free radical cyclization was realized allowing access to the (±)-9,10-bis-epi-stemoamide. This reaction was highly stereoselective and allowed the control of three of the four contiguous stereocenters present in the molecule.
Dual C(sp3)-H Functionalization of Cyclic Ethers via Singlet Oxygen-Mediated Ring Opening and Ring Closing
Yuan, Xu,Yu, Xianglin,He, Kun,Zhang, Ruihan,Xiao, Weilie,Lin, Jun,Zhan, Zhajun,Cheng, Xiaohong,Shao, Zhihui,Jin, Yi
supporting information, p. 8267 - 8272 (2021/10/25)
A metal-free dual C(sp3)-H bond functionalization of saturated cyclic ethers via photooxidative singlet oxygen-mediated ring opening and ring closing has been developed, providing a method for generating hydrobenzofurans/pyrans/dioxins. Mechanistic studies have confirmed that ring-opening intermediates were effectively generated by singlet oxygen-mediated C(sp3)-H activation and efficiently reacted with aldehydes and activated methylene compounds to form a wide array of products with high diastereoselectivities (up to >95:5 dr). This study is a rare example of α,β-dual C(sp3)-H bond functionalization of ethers.
Synthesis of (E)-α-hydroxyethyl-α,β-unsaturated aldehydes by the reaction of tetrahydrofuran and aromatic aldehydes
Shi, Yong-Sen,Liu, Jian-Feng,Wu, Xiao-Lan,Ke, De-Hong,Xu, Sheng
supporting information, (2021/08/13)
Although α-functionalized α,β-unsaturated aldehydes have important applications in biomedicine, there are few reports on their synthesis. In this article, a new domino reaction for the synthesis of (E)-α-hydroxyethyl-α,β-unsaturated aldehydes was introduced, in which tetrahydrofuran (THF) used as carbonyl block. The first step is an oxidation of THF to 2-hydroxytetrahydrofuran (HTHF) and then it was condensed with ethanolamine under acid catalysis to obtain imine intermediate, which was further isomerized to enamines and used as nucleophiles to attack aldehydes. This is a simple and efficient way for the preparation of (E)-α-hydroxyethyl-α,β-unsaturated aldehydes with notable advantages of a simple procedure, widespread availability of the substrates.