1007-32-5Relevant academic research and scientific papers
Rhodium-Catalyzed Room Temperature C-C Activation of Cyclopropanol for One-Step Access to Diverse 1,6-Diketones
Ghosh, Asit,Pati, Bedadyuti Vedvyas,Ravikumar, P. C.
, (2020)
A rhodium-catalyzed room temperature C-C activation of cyclopropanol has been demonstrated for the single-step synthesis of a range of electronically and sterically distinct 1,6-diketones. This reaction proceeds efficiently in shorter reaction time following a highly atom-economical pathway. To illustrate the synthetic potential of 1,6-diketones, aldol and macrocyclization reactions have been successfully demonstrated. Preliminary mechanistic studies revealed the involvement of nonradical pathways.
Development of a metal-free oxidation of alcohols with dimethyl sulfoxide (DMSO) activated by tosyl chloride
Saadati, Fariba,Yousefi, Kobra
, p. 2818 - 2825 (2014)
In this article we propose an efficient metal-free method for the mild oxidation of alcohols using dimethyl sulfoxide/tosyl chloride at ambient temperature. The procedure described here is an easy and practical method for the oxidation of primary, secondary, allylic, and benzylic alcohols into their corresponding aldehydes and ketones. The notable advantages of this protocol are mild reaction conditions, good yields and selectivity, and simple workup with minimal waste containing no metallic components. The mechanism of the transformation is also investigated.
A convenient catalytic oxidative 1,2-shift of arylalkenes for preparation of α-aryl ketones mediated by NaI
Zhu, Min,Zhao, Yang
, p. 248 - 250 (2015)
Using a catalytic amount of NaI and a stoichiometric oxidant Oxone@, a convenient procedure has been developed for the catalytic oxidative 1,2-shift of arylalkenes in CH3CN/H2O at room temperature, which provides the corresponding α-aryl ketones in moderate to good yields. In this protocol, sodium iodide is first oxidized into hypoiodous acid, which reacts with arylalkene to afford iodohydrin. Then, the iodohydrin is transformed into the α-aryl ketone via an oxidative 1,2-shift rearrangement.
Palladium-catalyzed aerobic oxidative coupling of allylic alcohols with anilines in the synthesis of nitrogen heterocycles
Kumar, Gangam Srikanth,Singh, Diksha,Kumar, Manish,Kapur, Manmohan
, p. 3941 - 3951 (2018)
We report herein an unprecedented and expedient Pd-catalyzed oxidative coupling of allyl alcohols with anilines to afford β-amino ketones which are converted into substituted quinolines in a one-pot fashion. The exclusive preference for N-alkylation over N-allylation makes this approach unique when compared to those reported in literature. Detailed mechanistic investigations reveal that the conjugate addition pathway was the predominant one over the allylic amination pathway. The notable aspects of the present approach are the use of readily available, bench-stable allyl alcohols and molecular oxygen as the terminal oxidant, in the process dispensing the need for unstable and costly enones. Further, we explored the synthetic utility of β-amino ketones through an intramolecular α-arylation methodology and a one-pot domino annulation, thereby providing rapid access to indolines and quinolines.
Electrochemical synthesis of ketones from acid chlorides and alkyl and aryl halides catalysed by nickel complexes
Marzouk, H.,Rollin, Y.,Folest, J. C.,Nedelec, J. Y.,Perichon, J.
, p. C47 - C50 (1989)
The nickel-catalysed electrochemical cross-coupling of acid chlorides and alkyl or aryl halides in acetonitrile affords unsymmetric ketones in good to high yields.The reaction can be performed under very simple and mild conditions in a diaphragmless cell.A zinc rod as the sacrificial anode has been found to be the most efficient.
Reactions of aldehydes with polymer-supported selenoalkylidenetriphenylphosphoranes. A facile method for the synthesis of carbonyl compounds
Huang, Xian,Sheng, Shou-Ri
, p. 9035 - 9037 (2001)
The transylidation reactions of polymer-bound selenium bromide with alkylidenetriphenylphosphoranes 1 gave resin 2, which is sufficiently reactive to undergo Wittig-type reactions to afford the vinylic selenide resins 3. Cleavage gave ketones and aldehydes under different conditions.
Rational Design of a Metallocatalytic Cavitand for Regioselective Hydration of Specific Alkynes
Endo, Naoki,Inoue, Mami,Iwasawa, Tetsuo
, p. 1136 - 1140 (2018)
The synthesis of a functionalized supramolecular cavitand with inwardly oriented AuI and P=O moieties was explored, including its catalytic proclivity in the selective hydration of internal alkynes. The cavitand works as a supramolecular flask device: AuI coordinates to the triple bond, the P=O moiety connects with a H2O molecule, and the cavity favors folding of a single alkynyl side chain. Several tests of different substrate patterns indicated that the cavity was substrate specific, similar to enzymatic catalysis.
Evaluation of the Catalytic Capability of cis- and trans-Diquinoxaline Spanned Cavitands
Inoue, Mami,Kamiguchi, Shinsuke,Ugawa, Katto,Hkiri, Shaima,Bouffard, Jules,Sémeril, David,Iwasawa, Tetsuo
, p. 6261 - 6268 (2019)
Three new cis-diquinoxaline spanned cavitands were successfully synthesized. These cis-diphosphinated derivatives were applied in homogeneous gold-catalyzed dimerization and hydration of alkynes as well as rhodium-catalyzed styrene hydroformylation. The results were ranked with those obtained with their trans-diphosphinated isomeric analogues. The structure-activity relationship employing these two cavitands reveals that the cis- or trans-positioning of the catalyst centers directly influences cooperation between the two metallic atoms to control catalytic activity, reaction profile, and product selectivity. This comparative study provides us an intellectual basis for future catalytic cavitand chemistry and homogeneous catalysis.
Deracemization and Stereoinversion of Alcohols Using Two Mutants of Secondary Alcohol Dehydrogenase from Thermoanaerobacter pseudoethanolicus
Hamdan, Samir M.,Musa, Musa M.,Nafiu, Sodiq A.,Takahashi, Etsuko,Takahashi, Masateru
, (2020)
We developed a one-pot sequential two-step deracemization approach to chiral alcohols using two mutants of Thermoanaerobacter pseudoethanolicus secondary alcohol dehydrogenase (TeSADH). This approach relies on consecutive non-stereospecific oxidation of alcohols and stereoselective reduction of their prochiral ketones using two mutants of TeSADH with poor and good stereoselectivities, respectively. More specifically, W110G TeSADH enables a non-stereospecific oxidation of alcohol racemates to their corresponding prochiral ketones, followed by W110V TeSADH-catalyzed stereoselective reduction of the resultant ketone intermediates to enantiopure (S)-configured alcohols in up to > 99 percent enantiomeric excess. A heat treatment after the oxidation step was required to avoid the interference of the marginally stereoselective W110G TeSADH in the reduction step; this heat treatment was eliminated by using sol-gel encapsulated W110G TeSADH in the oxidation step. Moreover, this bi-enzymatic approach was implemented in the stereoinversion of (R)-configured alcohols, and (S)-configured alcohols with up to > 99 percent enantiomeric excess were obtained by this Mitsunobu-like stereoinversion reaction.
Novel Electrophilic Species Equivalent to α-Keto Cations. Reactions of O,O-Diprotonated Nitro Olefins with Benzenes Yield Arylmethyl Ketones
Okabe, Kazuaki,Ohwada, Tomohiko,Ohta, Toshiharu,Shudo, Koichi
, p. 733 - 734 (1989)
The N,N-dihydroxyiminium carbenium ions formed by O,O-diprotonation of nitro olefins in a strong acid, trifluoromethanesulfonic acid (TFSA), are discrete and novel dipositively charged species.The dications formed from α-substitited nitroethylenes are reactive electrophiles to give α-arylated ketones in high yields.This constitutes a versatile synthetic method for the preparation of α-arylated ketones, which are difficult to synthesize by the conventional Friedel-Crafts reactions.
