1585-03-1Relevant academic research and scientific papers
Chiral bicyclo[3.3.1]-3,7-dioxanonane derivatives: Study of crystallization mode and conformational dynamics in solution
Uncu?a, Cornelia,Bartha, Emeric,Gherase, Drago?,Loas, Ioan Andrei,Teodorescu, Florina,Varga, Richard A.,Vanthuyne, Nicolas,Roussel, Christian,Berg, Ulf
, p. 20 - 30 (2011)
A homologous series of chiral bis-ketals and mixed hemiketal-ketals with rigid bicyclo[3.3.1]-3,7-dioxanonane skeleton has been prepared. The crystallization mode (conglomerate or racemic compound) was established by chiral HPLC with double UV/polarimetri
Palladium-Mediated Tandem Isomerization-Methylenation of Allyl Alcohols: One-Pot Synthesis of 1,5-Diketones
Samser, Shaikh,Mohapatra, Omkar,Biswal, Priyabrata,Venkatasubbaiah, Krishnan
, p. 13744 - 13753 (2021/10/12)
A novel methodology for the synthesis of 1,5-diketones through a one-pot isomerization-methylenation of a variety of allylic alcohols has been established for the first time. This methodology utilizes commercially available palladium acetate and easily accessible BINOL phosphoric acid. Both isomerization of allylic alcohol and oxidation of methanol occurred through a single catalyst. The practical utility of the methodology has been shown by synthesizing substituted pyridines via sequential addition. Mechanistic investigation reveals the isomerization of allylic alcohols to the corresponding ketone, which ultimately undergoes methylenation, leading to 1,5-diketones, having H2 and H2O as the only byproduct.
Cobalt(II)porphyrin-Mediated Selective Synthesis of 1,5-Diketones via an Interrupted-Borrowing Hydrogen Strategy Using Methanol as a C1 Source
Biswal, Priyabrata,Samser, Shaikh,Nayak, Prakash,Chandrasekhar, Vadapalli,Venkatasubbaiah, Krishnan
, p. 6744 - 6754 (2021/05/29)
A novel cobalt(II)porphyrin-mediated acceptorless dehydrogenation of methanol is reported for the first time. This methodology has been applied for the coupling of a variety of ketones with methanol to produce 1,5-diketones along with H2 and H2O as the environment friendly byproducts. This paradigm was also demonstrated for a one-pot synthesis of substituted pyridines using a sequential addition protocol where the 1,5-diketones were generated in situ. From many experiments including those involving deuterium labeling, it is proposed that protonated cobalt(II)porphyrin methoxide complex acts as an intermediate to generate formaldehyde along with a metal hydride.
Manganese catalyzed α-methylation of ketones with methanol as a C1 source
Bruneau-Voisine, Antoine,Pallova, Lenka,Bastin, Stéphanie,César, Vincent,Sortais, Jean-Baptiste
supporting information, p. 314 - 317 (2019/01/09)
The direct α-methylation of ketones with methanol under hydrogen borrowing conditions using a well-defined manganese PN3P complex as a pre-catalyst was, for the first time, achieved. The reactions typically proceed at 120 °C for 20 h with 3 mol% pre-catalyst loading and in the presence of NaOtBu (50 mol%) as base. The scope of the reaction was extended to the α-methylation of esters.
α-Methylation of Ketones with Methanol Catalyzed by Ni/SiO2-Al2O3
Charvieux, Aubin,Duguet, Nicolas,Métay, Estelle
supporting information, p. 3694 - 3698 (2019/06/13)
α-Methylation of ketones with methanol catalyzed by a cheap and easy to handle Ni/SiO2-Al2O3 was explored. After optimization of the reaction between propiophenone and methanol, the desired product was obtained in 95 % isolated yield. A wide range of ketones was methylated under the optimized conditions (16 examples). This procedure was extended to a three-component cross-benzylation-methylation of acetophenone.
Cobalt-Catalyzed α-Methoxymethylation and Aminomethylation of Ketones with Methanol as a C1 Source
Yang, Jingya,Chen, Shuwen,Zhou, Hongyan,Wu, Chengqi,Ma, Ben,Xiao, Jianliang
supporting information, p. 6774 - 6779 (2018/10/25)
Using methanol as a sustainable C1 source, cobalt-catalyzed α-methoxymethylation and α-aminomethylation of ketones have been developed. With cheap CoCl2·6H2O as catalyst and TBHP as oxidant, the methoxymethylated products were obtained within a short reaction time in up to 91% yield. Based on the observed reversibility of methoxy adduct to enone, the α-aminomethylation of ketones was then achieved by a one-pot methylenation/aza-Michael addition sequence. In addition, an easy way to convert α-methoxymethyl ketones to α-aminomethyl ketones has been discovered.
Short and simple synthesis of chelating bis-ethers and bis-amines in the bicyclo[3.3.1]nonane series
Chau, Felix H. V.,Corey
, p. 2581 - 2583 (2007/10/03)
A remarkably simple process for the synthesis of a series of rigid bicyclic diethers and diamines is described.
Thiomethylation of ketones by sodium sulphide and formaldehyde
Ulendeyeva,Bayeva,Lyapina,Shmakov,Galkin
, p. 177 - 186 (2007/10/03)
The thiomethylation of propanol, butanol, cyclohexanone and acetophenone with a mixture of formaldehyde and sodium sulphide proceeds at 20°C and normal pressure for 1-7 hr. It has been established that the reactivity of ketones increases in the order butanone-cyclohexanone-propanone-acetophenone. The conversion of sodium sulphide depends on its initial concentration, the nature of the ketone, and the presence in the reaction medium of sodium hydroxide and ethyl alcohol. It has been shown that the reaction proceeds with the preferential formation of keto- and diketosulphides.
ONE-METHYLENE INCORPORATED DIMERIZATION REACTION OF KETONE ENOLATES. 1. A NEW ROUTE TO 1,5-DIKETONES FROM KETONES HAVING α-ACTIVE HYDROGEN ON ONE SIDE
Kiyooka, Syun-ichi,Yamashita, Tsuneo,Tashiro, Jun-ichi,Takano, Kazuyuki,Uchio, Yasuto
, p. 5629 - 5632 (2007/10/02)
A novel reaction of ketone enolate with dimethylformamide (DMF) to give 1,5-diketone has been found.It is a dimerization of ketone enolates accompanying the incorporation of one-methylene from DMF.
