886-38-4Relevant academic research and scientific papers
Cyclopropeniminium Ions Exhibit Unique Reactivity Profiles with Bioorthogonal Phosphines
Heiss, Tyler K.,Prescher, Jennifer A.
, p. 7443 - 7448 (2019)
We report a new ligation of cyclopropeniminium ions with bioorthogonal phosphines. Cyclopropeniminium scaffolds are sufficiently stable in biological media and, unlike related isomers, react with functionalized phosphines via formal 1,2-addition to a I-system. The ligation can be performed in aqueous solution and is compatible with existing bioorthogonal transformations. Such mutually compatible reactions are useful for multicomponent labeling.
Synthesis, characterization, and oxidation electrochemistry of some novel 1,2-dithiol-3-ones and 1,2-dithiol-3-thiones containing aryl and metallocenyl fragments
Sánchez García, Jessica J.,Joo-Cisneros, Rene S.,García-Bassoco, David,Flores-Alamo, Marcos,Stivalet, José M. Méndez,García-Valdés, Jesús,Klimova, Elena I.
, (2021/05/17)
A new synthesis method was established for 1,2-dithiol-3-ones and 1,2-dithiol-3-thiones, from different cyclopropenones: diphenyl (a), bis-(4-methoxyphenyl (b), diferrocenyl (c) and diruthenocenyl (d), in the presence of elemental sulfur with yields of the 5a-d (35–57%), or in the presence of the additive NaHS, with yields of the 5a-d (45–72%) and 6a-d (10–18%). The characterization of the new compounds was conducted by IR, 1H and 13C NMR spectroscopy, elemental analysis, mass-spectrometry. In addition, X-ray crystallographic analysis of the compounds 5a,b,d was conducted. The redox properties of the heterocyclic compounds were investigated using cyclic (CV), differential pulse (DPV) and square wave (SWV) voltammetries.
Fully Substituted Conjugate Benzofuran Core: Multiyne Cascade Coupling and Oxidation of Cyclopropenone
Yao, Liangliang,Hu, Qiong,Bao, Li,Zhu, Wenjing,Hu, Yimin
supporting information, p. 4971 - 4975 (2021/06/30)
An unprecedented C═C double bond cleavage of cyclopropenone and dioxygen activation by multiyne cascade coupling has been developed. This chemistry provides a novel, simple, and efficient approach to synthesize fully substituted conjugate benzofuran derivatives from simple substrates under mild conditions. The density functional theory (DFT) calculations reveal that the unique homolytic cleavages of cyclopropenone and molecular oxygen are crucial to the success of this reaction.
Palladium-Catalyzed C-C Bond Activation of Cyclopropenone: Modular Access to Trisubstituted α,β-Unsaturated Esters and Amides
Nanda, Tanmayee,Biswal, Pragati,Pati, Bedadyuti Vedvyas,Banjare, Shyam Kumar,Ravikumar, Ponneri Chandrababu
, p. 2682 - 2695 (2021/02/01)
Strain-driven palladium/N-heterocyclic carbene-catalyzed C-C bond activation of diphenylcyclopropenone (DPC) has been explored for one-step access to trisubstituted α,β-unsaturated esters and amides. The designed transformation works under mild conditions providing exclusively a single stereoisomer. Mechanistic studies support the oxidative addition of the C-C bond of cyclopropenone to in-situ-generated Pd(0) intermediate. We have proved that vinylic hydrogen in the product is coming from phenol/aniline through deuterium-labeling studies. Late-stage functionalization of bioactive molecules such as procaine, estrone, and hymecromone demonstrates the robustness of this protocol.
A Palladium-Catalyzed Cascade C-C Activation of Cyclopropenone and Carbonylative Amination: Easy Access to Highly Functionalized Maleimide Derivatives
Nanda, Tanmayee,Ravikumar, P. C.
supporting information, (2020/02/15)
We describe herein the first report on palladium-catalyzed C-C bond activation of cyclopropenone and concomitant carbonylative amination to produce maleimides. The interesting aspect of this reaction is that the sacrificial elimination of carbon monoxide from the substrate is efficiently recaptured by one of the intermediates in the catalytic cycle for the formation of maleimides. 18O isotopic studies confirmed that the source of carbon monoxide is from cyclopropenone.
Rh(III)-Catalyzed [3 + 3] Annulation Reaction of Cyclopropenones and Sulfoxonium Ylides toward Trisubstituted 2-Pyrones
Zhou, Peng,Yang, Wei-Tao,Rahman, Anis Ur,Li, Guigen,Jiang, Bo
, p. 360 - 366 (2019/11/14)
A new Rh(III)-catalyzed [3 + 3] annulation reaction between cyclopropenones and β-ketosulfoxonium ylides has been reported, enabling metal carbene insertion to access a wide range of trisubstituted 2-pyrones with moderate to excellent yields via C-C single-bond cleavage, in which sulfoxonium ylides serve as potential safe precursors of metal carbenes. This reaction occurred under redox-neutral conditions with a broad substrate scope.
Cyclopropenium-Activated DMSO for Swern-Type Oxidation
Guo, Tianfo,Gao, Yu,Li, Zhenjiang,Liu, Jingjing,Guo, Kai
supporting information, p. 329 - 332 (2019/02/12)
Swern oxidation is widely used to convert alcohols into their corresponding carbonyl compounds. However, the conventional method with use of the volatile oxalyl chloride as an activator requires the reaction to be conducted below -60 °C. We discovered that 3,3-dichloro-1,2-diphenylcyclopropene (DDC) can be used as a new activator for Swern-type oxidations of alcohols, which can be conducted at -20 °C. This new protocol features mild and fast reactions with easy operation. Furthermore, the activator DDC is easy to handle, and diphenylcyclopropenone can be recovered quantitively. This new type of Swern oxidation shows a broad scope of substrates including benzylic, allylic, aliphatic, and biobased alcohols, and gives high yields of up to 93%.
Organocatalytic Regiodivergent C?C Bond Cleavage of Cyclopropenones: A Highly Efficient Cascade Approach to Enantiopure Heterocyclic Frameworks
Cao, Jian,Fang, Ran,Liu, Jin-Yu,Lu, Hong,Luo, Yong-Chun,Xu, Peng-Fei
supporting information, p. 18863 - 18867 (2018/11/23)
Here a highly efficient cascade approach is reported that combines a cycloaddition reaction with a regioselective strain-release process to afford diverse heterocyclic frameworks through bifunctional catalysis. The cooperation of hydrogen-bonding network activation and a regiodivergent strain-assisted effect is the key to promoting this complex chemical transformation, leading to the generation of two different ring systems in high yields with excellent stereoselectivities. The reaction proceeded by a mechanism involving a “spring-loaded” intermediate with switchable C?C bond cleavages achieved by controllable ring-strain release. This reaction was also amenable to gram scale synthesis with only 0.1 mol % catalyst loading.
Organocatalyzed [3 + 2] Annulation of Cyclopropenones and β-Ketoesters: An Approach to Substituted Butenolides with a Quaternary Center
Li, Xuanyi,Han, Chunhua,Yao, Hequan,Lin, Aijun
supporting information, p. 778 - 781 (2017/03/01)
An unprecedented organocatalyzed [3 + 2] annulation of cyclopropenones and β-ketoesters has been developed. This reaction provides a direct approach to highly substituted butenolides with a quaternary center in moderate to good yields. The preliminary mechanism study verified that the enol intermediate is crucial to the reaction outcome and the intermolecular esterification and intramolecular Michael addition process were involved.
Cyclopropenone catalyzed substitution of alcohols with mesylate ion
Nacsa, Eric D.,Lambert, Tristan H.
supporting information, p. 38 - 41 (2013/03/28)
The cyclopropenone catalyzed nucleophilic substitution of alcohols by methanesulfonate ion with inversion of configuration is described. This work provides an alternative to the Mitsunobu reaction that avoids the use of azodicarboxylates and generation of hydrazine and phosphine oxide byproducts. This transformation is shown to be compatible with a range of functionality. A cyclopropenone scavenge strategy is demonstrated to aid purification.
