5682-46-2Relevant academic research and scientific papers
Synergistic Activation of Amides and Hydrocarbons for Direct C(sp3)–H Acylation Enabled by Metallaphotoredox Catalysis
Baik, Mu-Hyun,Choi, Seulhui,Hong, Soon Hyeok,Lee, Geun Seok,Won, Joonghee
, p. 16933 - 16942 (2020/08/03)
The utilizations of omnipresent, thermodynamically stable amides and aliphatic C(sp3)?H bonds for various functionalizations are ongoing challenges in catalysis. In particular, the direct coupling between the two functional groups has not been realized. Here, we report the synergistic activation of the two challenging bonds, the amide C?N and unactivated aliphatic C(sp3)?H, via metallaphotoredox catalysis to directly acylate aliphatic C?H bonds utilizing amides as stable and readily accessible acyl surrogates. N-acylsuccinimides served as efficient acyl reagents for the streamlined synthesis of synthetically useful ketones from simple C(sp3)?H substrates. Detailed mechanistic investigations using both computational and experimental mechanistic studies were performed to construct a detailed and complete catalytic cycle. The origin of the superior reactivity of the N-acylsuccinimides over other more reactive acyl sources such as acyl chlorides was found to be an uncommon reaction pathway which commences with C?H activation prior to oxidative addition of the acyl substrate.
Palladium catalyzed decarboxylative acylation of arylboronic acid with ethyl cyanoacetate as a new acylating agent: Synthesis of alkyl aryl ketones
Yousuf, Md,Das, Tuluma,Adhikari, Susanta
, p. 8763 - 8770 (2015/11/10)
Palladium catalyzed acylation of arylboronic acid containing various functional groups was performed efficiently by ethyl cyanoacetate/substituted ethyl cyanoacetate as the acylating agent in aqueous triflic acid medium. The alkyl aryl ketones were obtained in good to excellent yields, first by addition of arylboronic acid to the nitrile group of ethyl cyanoacetate and their derivatives, followed by in situ decarboxylation of the resulting β-ketoester.
Unexpected double benzylation of acetophenone under phase transfer catalysis conditions, acidity or π-π interaction effect?
Diez-Barra, Enrique,De la Hoz, Antonio,Loupy, Andre,Martinez-Gonzalez, Alfonso,Martinez-Merino, Victor,Merino, Sonia,Paugam, Renee,Sanchez-Verdu, Prado,Sansoulet, Jean,Torres, Jose
, p. 3659 - 3668 (2007/10/03)
A π-π interaction in the transition state of the benzylation of 1,3-diphenyl-1-propanone, the monobenzylation product of acetophenone, is proposed according to chemical, kinetic and theoretical approaches. Evidence for the existence of this kind of interaction in a transition state has been provided for the first time. The results obtained cannot be explained solely by the increased acidity but by considering the existence of a π-π interaction.
Direct formation of secondary and tertiary alkylzinc bromides and subsequent Cu(I)-mediated couplings
Rieke, Reuben D.,Hanson, Mark V.,Brown, Jeffrey D.,Niu, Q. Jason
, p. 2726 - 2730 (2007/10/03)
Secondary and tertiary alkylzinc bromides can be generated from the direct oxidative addition of Rieke zinc to secondary and tertiary alkyl bromides in high yield. These organozinc reagents have been found to undergo copper-catalyzed conjugate addition, cross-coupling with acid chlorides, and carbocupration to activated alkynes.
Direct formation of secondary and tertiary alkylzinc bromides
Hanson, Mark V.
, p. 7205 - 7208 (2007/10/02)
The direct formation of secondary and tertiary alkylzinc bromides can be accomplished under mild conditions from the direct oxidative addition of Rieke zinc to secondary and tertiary alkyl bromides including remote functionalized halides.
Additions of Alkyllanthanum Triflates to Carbonyl Compounds: Reactive Organometallic Nucleophiles
Collins, Scott,Hong, Yaping,Hoover, Gordon J.,Veit, Jennifer R.
, p. 3565 - 3568 (2007/10/02)
Addition of alkyl- or aryllithium compounds to lanthanum(III) triflate in ethereal solvents produces the title reagents 2 that undergo nucleophilic addition to carbonyl compounds under mild conditions.These reagents resemble alkylcerium halides in their reactions with enolizable carbonyl compounds but are more reactive.In particular, they are useful for the conversion of hindered, tertiary amides to the ketones. 1H NMR spectroscopy was employed to clarify mechanistic aspects of this addition process.The title reagents actually appear to be a mixture of several species; formulation of their structure has proven elusive.However, in the presence of a tertiary amide, these species react to give a single, tetrahedral intermediate, which is quite stable in solution.
ORGANOMETALLIC REACTIONS OF α-HALOIMINES AS A USEFUL TOOL IN ORGANIC SYNTHESIS
Kimpe, Norbert De,Corte, Bart De,Verhe, Roland,Buyck, Laurent De,Schamp, Niceas
, p. 1095 - 1098 (2007/10/02)
The reaction of organometallic reagents, e.g. alkyllithiums, cuprates and alkylcoppers, with α-haloimines gave selectively a variety of synthetically useful reactions, including coupling to 1,4-diimines, homologation, and production of heterocycles.
