89-98-5Relevant articles and documents
Transition metal-free oxidation of activated alcohols to aldehydes and ketones in 1,1,1,3,3,3-hexafluoro-2-propanol
Khaksar, Samad,Talesh, Saeed Mohammadzadeh
, p. 95 - 98 (2012)
A simple and convenient procedure for the oxidation of various benzylic, allylic and some aliphatic alcohols to their corresponding carbonyl compounds is described using sodium hypochlorite as the oxidant in 1,1,1,3,3,3-hexafluoro-2- propanol without use
Controlled reduction of activated primary and secondary amides into aldehydes with diisobutylaluminum hydride
Azeez, Sadaf,Kandasamy, Jeyakumar,Sabiah, Shahulhameed,Sureshbabu, Popuri
, p. 2048 - 2053 (2022/03/31)
A practical method is disclosed for the reduction of activated primary and secondary amides into aldehydes using diisobutylaluminum hydride (DIBAL-H) in toluene. A wide range of aryl and alkyl N-Boc, N,N-diBoc and N-tosyl amides were converted into the corresponding aldehydes in good to excellent yields. Reduction susceptible functional groups such as nitro, cyano, alkene and alkyne groups were found to be stable. Broad substrate scope, functional group compatibility and quick conversions are the salient features of this methodology.
Aerobic epoxidation of styrene over Zr-based metal-organic framework encapsulated transition metal substituted phosphomolybdic acid
Hu, Dianwen,Song, Xiaojing,Zhang, Hao,Chang, Xinyu,Zhao, Chen,Jia, Mingjun
, (2021/04/19)
Catalytic epoxidation of styrene with molecular oxygen is regarded as an eco-friendly alternative to producing industrially important chemical of styrene oxide (STO). Recent efforts have been focused on developing highly active and stable heterogeneous catalysts with high STO selectivity for the aerobic epoxidation of styrene. Herein, a series of transition metal monosubstituted heteropolyacid compounds (TM-HPAs), such as Fe, Co, Ni or Cu-monosubstituted HPA, were encapsulated in UiO-66 frameworks (denoted as TM-HPA@UiO-66) by direct solvothermal method, and their catalytic properties were investigated for the aerobic epoxidation of styrene with aldehydes as co-reductants. Among them, Co-HPA@UiO-66 showed relatively high catalytic activity, stability and epoxidation selectivity at very mild conditions (313 K, ambient pressure), that can achieve 82 % selectivity to STO under a styrene conversion of 96 % with air as oxidant and pivalaldehyde (PIA) as co-reductant. In addition, the hybrid composite catalyst can also efficiently catalyze the aerobic epoxidation of a variety of styrene derivatives. The monosubstituted Co atoms in Co-HPA@UiO-66 are the main active sites for the aerobic epoxidation of styrene with O2/PIA, which can efficiently converting styrene to the corresponding epoxide through the activation of the in-situ generated acylperoxy radical intermediate.
METHOD FOR OXIDATIVE CLEAVAGE OF COMPOUNDS WITH UNSATURATED DOUBLE BOND
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Paragraph 0071; 0077, (2021/07/10)
A method for oxidative cleavage of a compound with an unsaturated double bond is provided. The method includes the steps of: (A) providing a compound (I) with an unsaturated double bond, a trifluoromethyl-containing reagent, and a catalyst; wherein, the catalyst is represented by Formula (II): M(O)mL1yL2z??(II);wherein, M, L1, L2, m, y, z, R1, R2 and R3 are defined in the specification; and(B) mixing the compound with an unsaturated double bond and the trifluoromethyl-containing reagent to perform an oxidative cleavage of the compound with the unsaturated double bond by using the catalyst in air or under oxygen atmosphere condition to obtain a compound represented by Formula (III):
METHOD FOR OXIDATIVE CLEAVAGE OF COMPOUNDS WITH UNSATURATED DOUBLE BOND
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Paragraph 0053-0054; 0062-0063, (2021/03/19)
A method for oxidative cleavage of a compound with an unsaturated double bond is provided. The method comprises the following step: (A) providing a compound (I) with an unsaturated double bond, a reagent with trifluoromethyl, and a catalyst; wherein the catalyst is represented by the following formula (II): M(O)mL1yL2z (II); wherein, M, L1, L2, m, y, z, R1, R2 and R3 are defined in the specification; and (B) mixing the compound with an unsaturated double bond and the reagent with a trifluoromethyl to perform an oxidation of the compound with the unsaturated double bond by using the catalyst at air or an oxygen condition to get a compound presented as formula (III):
Samarium-based Grignard-type addition of organohalides to carbonyl compounds under catalysis of CuI
Liu, Chen,Liu, Yongjun,Qi, Yan,Song, Bin,Wang, Liang,Xiao, Shuhuan
supporting information, p. 6169 - 6172 (2021/06/30)
Grignard-type additions were readily achieved under the mediation of CuI (10 mol%) and samarium (2 equiv.) by employing various organohalides,e.g.benzyl, aryl, heterocyclic and aliphatic halides (Cl, Br or I), and diverse carbonyl compounds (e.g.carbonic esters, carboxylic esters, acid anhydrides, acyl chlorides, ketones, aldehydes, propylene epoxides and formamides) to afford alcohols, ketones and aldehydes, respectively, with high efficiency and chemoselectivity, in which the organosamarium intermediate might be involved.
Selective oxidation of alkenes to carbonyls under mild conditions
Huo, Jie,Xiong, Daokai,Xu, Jun,Yue, Xiaoguang,Zhang, Pengfei,Zhang, Yilan
supporting information, p. 5549 - 5555 (2021/08/16)
Herein, a practical and sustainable method for the synthesis of aldehydes, ketones, and carboxylic acids from an inexpensive olefinic feedstock is described. This transformation features very sustainable and mild conditions and utilizes commercially available and inexpensive tetrahydrofuran as the additive, molecular oxygen as the sole oxidant and water as the solvent. A wide range of substituted alkenes were found to be compatible, providing the corresponding carbonyl compounds in moderate-to-good yields. The control experiments demonstrated that a radical mechanism is responsible for the oxidation reaction.
Hydroxyl radical-mediated oxidative cleavage of CC bonds and further esterification reaction by heterogeneous semiconductor photocatalysis
Hong, Mei,Jia, Rui,Miao, Hongyan,Ni, Bangqing,Niu, Tengfei,Wang, Hui
, p. 6591 - 6597 (2021/09/10)
A hydroxyl radical-mediated aerobic cleavage of alkenes and further sequence esterification reaction for the preparation of carbonyl compounds have been developed by using tubular carbon nitride (TCN) as a general heterogeneous photocatalyst under an oxygen atmosphere with visible light irradiation. This protocol has an excellent substrate scope and gives the desired aldehydes, ketones and esters in moderate to high yields. Importantly, this metal-free procedure employed photogenerated hydroxyl radicals in situ as green oxidation active species, avoiding the present additional initiators. The reaction could be carried out under solar light irradiation and was applicable to large-scale reactions. Furthermore, the recyclable TCN catalyst could be used several times without a significant loss of activities.
Thiol-initiated photocatalytic oxidative cleavage of the C=C bond in olefins and its extension to direct production of acetals from olefins
Wang, Xinglin,Li, Yuanyuan,Li, Zhaohui
, p. 1000 - 1006 (2021/02/26)
The oxidative cleavage of olefins to produce aldehydes/ketones is an important reaction in organic syntheses. In this manuscript, a mild and operationally simple protocol for the aerobic oxidation of olefins to produce carbonyl compounds was realized over ZnIn2S4under visible light, using air as the oxidant and a thiol as the initiator. It was proposed that the photogenerated holes over ZnIn2S4attack the thiol to produce thiyl radicals, which initiate the oxidative cleavage of the C=C bond in olefins to produce aldehydes/ketones. By further coupling with the condensation between the as-obtained aldehydes/ketones and alcohols, this strategy can also be applied to the production of different acetals directly from the olefins. This study demonstrates a new pathway to realize the oxidative cleavage of olefins to produce aldehydes/ketones, and also provides a new protocol for the production of acetals directly from the olefins.
Visible-Light-Driven Oxidative Cleavage of Alkenes Using Water-Soluble CdSe Quantum Dots
Li, Jianing,Zhao, Jingnan,Ma, Cunfei,Yu, Zongyi,Zhu, Hongfei,Yun, Lei,Meng, Qingwei
, p. 4985 - 4992 (2021/10/16)
The oxidative cleavage of C=C bonds is an important chemical reaction, which is a popular reaction in the photocatalytic field. However, high catalyst-loading and low turnover number (TON) are general shortcomings in reported visible-light-driven reactions. Herein, the direct oxidative cleavage of C=C bonds through water-soluble CdSe quantum dots (QDs) is described under visible-light irradiation at room temperature with high TON (up to 3.7×104). Under the same conditions, water-soluble CdSe QDs could also oxidize sulfides to sulfoxides with 51–84 % yields and TONs up to 3.4×104. The key features of this photocatalytic protocol include high TONs, wide substrates scope, low catalyst loadings, simple and mild reaction conditions, and molecular O2 as the oxidant.
