643-75-4Relevant articles and documents
Structural insights into the desymmetrization of bulky 1,2-dicarbonyls through enzymatic monoreduction
Rabuffetti, Marco,Cannazza, Pietro,Contente, Martina Letizia,Pinto, Andrea,Romano, Diego,Hoyos, Pilar,Alcantara, Andres R.,Eberini, Ivano,Laurenzi, Tommaso,Gourlay, Louise,Di Pisa, Flavio,Molinari, Francesco
supporting information, (2021/01/25)
Benzil reductases are dehydrogenases preferentially active on aromatic 1,2-diketones, but the reasons for this peculiar substrate recognition have not yet been clarified. The benzil reductase (KRED1-Pglu) from the non-conventional yeast Pichia glucozyma showed excellent activity and stereoselectivity in the monoreduction of space-demanding aromatic 1,2-dicarbonyls, making this enzyme attractive as biocatalyst in organic chemistry. Structural insights into the stereoselective monoreduction of 1,2-diketones catalyzed by KRED1-Pglu were investigated starting from its 1.77 ? resolution crystal structure, followed by QM and classical calculations; this study allowed for the identification and characterization of the KRED1-Pglu reactive site. Once identified the recognition elements involved in the stereoselective desymmetrization of bulky 1,2-dicarbonyls mediated by KRED1-Pglu, a mechanism was proposed together with an in silico prediction of substrates reactivity.
Recyclable heterogeneous gold(I)-catalyzed oxidation of internal acylalkynes: Practical access to vicinal tricarbonyls
Hu, Wenli,Huang, Bin,Niu, Bingbo,Cai, Mingzhong
supporting information, (2021/03/16)
A highly efficient heterogeneous gold(I)-catalyzed oxidation of internal acylalkynes has been developed using 2,6-dichloropyridine N-oxide as the oxidant in dichloromethane (CH2Cl2) at room temperature, providing a novel and practical approach for the construction of diverse vicinal tricarbonyls such as α,β-diketoesters, 1,2,3-triketones, and α,β-diketoamides in good to excellent yields. The heterogeneous gold(I) catalyst can be readily obtained via a simple preparative procedure from commercially available reagents and recovered by filtration of the reaction mixture and reused up to seven times without significant loss of catalytic efficiency.
Iodine-catalyzed α,β-dehydrogenation of ketones and aldehydes generating conjugated enones and enals
Cao, Yuanjie,Chen, Tieqiao,Huang, Tianzeng,Liu, Long
, p. 8697 - 8701 (2020/06/08)
A transition metal-free α,β-dehydrogenation of ketones and aldehydes was developed. This reaction was conducted in a facile I2/KI/DMSO system to produce the corresponding unsaturated compounds in good to high yields. The gram-scale experiment also indicated the potential synthetic value of this new reaction in organic synthesis. In the reaction, DMSO acted as both solvent and mild oxidant.
Oxidation of β-Ketoamides: The Synthesis of Vicinal Tricarbonyl Amides
Liu, Yueyang,Zhang, Zhiguo,Wan, Yameng,Zhang, Guisheng,Li, Zhonglian,Bi, Jingjing,Ma, Nana,Liu, Tongxin,Liu, Qingfeng
, p. 3901 - 3907 (2017/04/11)
A facile and direct oxidative reaction for the synthesis of vicinal tricarbonyl amides in moderate to excellent yields (53-88%) was developed starting from readily available β-ketoamides in the presence of phenyliodine(III) bis(trifluoroacetate). The resu
LiBr/β-CD/IBX/H2O-DMSO: A new approach for one-pot biomimetic regioselective ring opening of chalcone epoxides to bromohydrins and conversion to 1,2,3-triketones
Verma, Nishant,Kumar, Sumit,Ahmed, Naseem
supporting information, p. 1110 - 1120 (2017/05/25)
Highly regioselective ring cleavage of chalcone epoxides to bromohydrins has been carried out in good yields with LiBr in the presence of β-CD using DMSO-H2O as solvent system. The ring-opened product, i.e., bromohydrin, was well adapted to IBX-mediated oxidation in such a fashion that the bromohydrins are transformed to their corresponding 1,2,3-triketones in moderate-to-good yields in one pot.
Anion Effects in Oxidative Aliphatic Carbon-Carbon Bond Cleavage Reactions of Cu(II) Chlorodiketonate Complexes
Saraf, Sushma L.,Mi?aczewska, Anna,Borowski, Tomasz,James, Christopher D.,Tierney, David L.,Popova, Marina,Arif, Atta M.,Berreau, Lisa M.
, p. 6916 - 6928 (2016/07/26)
Aliphatic oxidative carbon-carbon bond cleavage reactions involving Cu(II) catalysts and O2 as the terminal oxidant are of significant current interest. However, little is currently known regarding how the nature of the Cu(II) catalyst, including the anions present, influence the reaction with O2. In previous work, we found that exposure of the Cu(II) chlorodiketonate complex [(6-Ph2TPA)Cu(PhC(O)CClC(O)Ph)]ClO4 (1) to O2 results in oxidative aliphatic carbon-carbon bond cleavage within the diketonate unit, leading to the formation of benzoic acid, benzoic anhydride, benzil, and 1,3-diphenylpropanedione as organic products. Kinetic studies of this reaction revealed a slow induction phase followed by a rapid decay of the absorption features of 1. Notably, the induction phase is not present when the reaction is performed in the presence of a catalytic amount of chloride anion. In the studies presented herein, a combination of spectroscopic (UV-vis, EPR) and density functional theory (DFT) methods have been used to examine the chloride and benzoate ion binding properties of 1 under anaerobic conditions. These studies provide evidence that each anion coordinates in an axial position of the Cu(II) center. DFT studies reveal that the presence of the anion in the Cu(II) coordination sphere decreases the barrier for O2 activation and the formation of a Cu(II)-peroxo species. Notably, the chloride anion more effectively lowers the barrier associated with O-O bond cleavage. Thus, the nature of the anion plays an important role in determining the rate of reaction of the diketonate complex with O2. The same type of anion effects were observed in the O2 reactivity of the simple Cu(II)-bipyridine complex [(bpy)Cu(PhC(O)C(Cl)C(O)Ph)ClO4] (3).
Reversible capture and release of aromatic amines by vicinal tricarbonyl compound
Yuki, Tatsuya,Yonekawa, Morio,Furusho, Yoshio,Sei, Yoshihisa,Tomita, Ikuyoshi,Endo, Takeshi
, p. 2868 - 2873 (2016/05/19)
In this paper, we report reversible capture and release of aromatic amines by diphenylpropanetrione (DPPT). Addition of aromatic amines to the central carbonyl group occurred readily at ambient temperature to provide the aromatic amine adducts of DPPT (DPPT-aromatic amines), which has a hemiaminal structure. On the other hand, washing a solution of DPPT-aromatic amine with diluted hydrochloric acid (HCl) enabled successful recovery of DPPT to demonstrate the reversible nature of this system.
Facile synthesis of 1,2,3-tricarbonyls from 1,3-dicarbonyls mediated by cerium(IV) ammonium nitrate
Sivan, Akhil,Deepthi, Ani
supporting information, p. 1890 - 1893 (2014/03/21)
A mild and efficient protocol for the synthesis of vicinal tricarbonyl compounds from β-dicarbonyls in a single step using cerium(IV) ammonium nitrate as a catalytic oxidant is described. Ease of execution, wide substrate scope and the suitability for the synthesis of commercially important compounds like ninhydrin, alloxan and oxoline make this reaction particularly noteworthy.
DDQ-mediated oxidation of sp3 C-H bond for the direct synthesis of vicinal tricarbonyl compounds Dedicated to academician Li-Xin Dai on the occasion of his 90th birthday
Wang, Zheng-Lin,An, Xing-Lan,Ge, Li-Shi,Jin, Jing-Hai,Luo, Xiaoyan,Deng, Wei-Ping
, p. 3788 - 3792 (2014/05/20)
A facile and direct synthetic method was developed for the construction of vicinal tricarbonyl compounds (VTCs) in moderate to excellent yields (46-92%), by treating the readily available 1,3-dicarbonyl compounds with 2,2,6,6-tetramethylpiperidine-1-oxyl
CAN-catalyzed rapid C-O bond formation towards α-aminoxylation of ketones
Feng, Peng,Song, Song,Zhang, Li-He,Jiao, Ning
supporting information, p. 2717 - 2720 (2015/01/08)
A simple and efficient approach towards α-oxyaminated ketones has been developed through CAN-catalyzed C-O bond formation with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO). The environmentally friendly transformation is practical due to the use of commercial available catalyst, easy operating procedures, the broad substrate scope, and short reaction time.
