4981-63-9Relevant articles and documents
Rh-Catalyzed Coupling of Aldehydes with Allylboronates Enables Facile Access to Ketones
Zhang, Kezhuo,Huang, Jiaxin,Zhao, Wanxiang
supporting information, (2022/02/21)
We present herein a novel strategy for the preparation of ketones from aldehydes and allylic boronic esters. This reaction involves the allylation of aldehydes with allylic boronic esters and the Rh-catalyzed chain-walking of homoallylic alcohols. The key to this successful development is the protodeboronation of alkenyl borylether intermediate via a tetravalent borate anion species in the presence of KHF2 and MeOH. This approach features mild reaction conditions, broad substrate scope, and excellent functional group tolerance. Mechanistic studies also supported that the tandem allylation and chain-walking process were involved.
Stepwise benzylic oxygenation via uranyl-photocatalysis
Hu, Deqing,Jiang, Xuefeng
supporting information, p. 124 - 129 (2022/01/19)
Stepwise oxygenation at the benzylic position (1°, 2°, 3°) of aromatic molecules was comprehensively established under ambient conditions via uranyl photocatalysis to produce carboxylic acids, ketones, and alcohols, respectively. The accuracy of the stepwise oxygenation was ensured by the tunability of catalytic activity in uranyl photocatalysis, which was adjusted by solvents and additives demonstrated through Stern–Volmer analysis. Hydrogen atom transfer between the benzylic position and the uranyl catalyst facilitated oxygenation, further confirmed by kinetic studies. Considerably improved efficiency of flow operation demonstrated the potential for industrial synthetic application.
Iridium-Catalyzed Asymmetric Hydrogenation of α-Fluoro Ketones via a Dynamic Kinetic Resolution Strategy
Tan, Xuefeng,Wen, Jialin,Zeng, Weijun,Zhang, Xumu
supporting information, p. 7230 - 7233 (2020/10/02)
The discrimination of a fluorine atom from a hydrogen atom has been challenging in asymmetric catalysis. We herein report iridium-catalyzed hydrogenation of α-fluoro ketones using a strategy of dynamic kinetic resolution. Both enantiomeric and diastereomeric selectivities were satisfactory in the preparation of β-fluoro alcohols. The DFT calculation revealed a C-F···Na charge-dipole interaction in the transition state of hydride transfer. This noncovalent interaction would be responsible for the diastereomeric control.
Manganese PNP-pincer catalyzed isomerization of allylic/homo-allylic alcohols to ketones-activity, selectivity, efficiency
Xia, Tian,Spiegelberg, Brian,Wei, Zhihong,Jiao, Haijun,Tin, Sergey,Hinze, Sandra,De Vries, Johannes G.
, p. 6327 - 6334 (2019/11/20)
We report the first manganese catalyzed isomerization of allylic alcohols to produce the corresponding carbonyl compounds. The ligand plays a decisive role in the efficiency of this reaction. Very high conversions could be obtained using a solvent-free reaction system. A detailed DFT study reveals a self-dehydrogenation/hydrogenation reaction mechanism which was verified by the isolation of the α,β-unsaturated ketone as intermediate and a deuterium labeling experiment. It also provided a rationale for the observed selectivity and the higher efficiency of phenyl over isopropyl substitution.
Additive-Free Isomerization of Allylic Alcohols to Ketones with a Cobalt PNP Pincer Catalyst
Spiegelberg, Brian,Dell'Acqua, Andrea,Xia, Tian,Spannenberg, Anke,Tin, Sergey,Hinze, Sandra,de Vries, Johannes G.
supporting information, p. 7820 - 7825 (2019/05/22)
Catalytic isomerization of allylic alcohols in ethanol as a green solvent was achieved by using air and moisture stable cobalt (II) complexes in the absence of any additives. Under mild conditions, the cobalt PNP pincer complex substituted with phenyl groups on the phosphorus atoms appeared to be the most active. High rates were obtained at 120 °C, even though the addition of one equivalent of base increases the speed of the reaction drastically. Although some evidence was obtained supporting a dehydrogenation–hydrogenation mechanism, it was proven that this is not the major mechanism. Instead, the cobalt hydride complex formed by dehydrogenation of ethanol is capable of double-bond isomerization through alkene insertion–elimination.
Synthetic method of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) butanone
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Paragraph 0026; 0050-0052; 0078-0080, (2018/09/08)
The invention discloses a synthetic method of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) butanone. The synthetic method comprises the following steps: (1) carrying out a Friedel-Crafts reaction on chlorobenzene with n-butyryl chloride under the catalysis of aluminium trichloride to obtain a compound I; (2) carrying out a bromination reaction on the compound I with bromine under the action ofa catalytic oxidizing agent to obtain a compound II; (3) carrying out a substitution reaction on the compound II with dimethylamine to obtain a compound III; (4) carrying out a quaternization reactionon the compound III with benzyl chloride to obtain a compound IV; (5) carrying out a substitution reaction on the compound IV with morpholine under the action of a composite catalyst to obtain a compound V; and (6) carrying out a rearrangement reaction on the compound V under the action of an alkali so as to obtain the 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) butanone. The synthetic methodprovided by the invention has the advantages of mild technological condition, simple operation, high selectivity and high total yield.
Palladium-Catalyzed Carbonylative Coupling of Aryl Iodides with Alkyl Bromides: Efficient Synthesis of Alkyl Aryl Ketones
Peng, Jin-Bao,Chen, Bo,Qi, Xinxin,Ying, Jun,Wu, Xiao-Feng
supporting information, p. 4153 - 4160 (2018/09/21)
Alkyl aryl ketones are important structures with applications in many areas of chemistry. Hence, efficient procedures for their production are particularly attractive. In this communication, a general and efficient carbonylative cross-coupling of aryl iodides and unactivated alkyl bromides is presented. By using a simple palladium catalyst, a series of alkyl aryl ketones were synthesized in moderate to excellent yields from readily available alkyl and aryl halides in an In-Ex tube with formic acid as the CO source. In this study both primary and secondary alkyl bromides/iodides were suitable coupling partners. Additionally, this method can also be employed for the late-stage functionalization of complex natural products and polyfunctionalized molecules. (Figure presented.).
Dirhodium(ii)/P(t-Bu)3 catalyzed tandem reaction of α,β-unsaturated aldehydes with arylboronic acids
Ma, Ziling,Wang, Yuanhua
supporting information, p. 7470 - 7476 (2018/10/24)
Phosphine ligated dirhodium(ii) acetate is advocated as a catalyst for the synthesis of aryl alkyl ketones by the tandem reaction of α,β-unsaturated aromatic or aliphatic aldehydes with arylboronic acids. This tandem procedure included arylation followed by the isomerization reaction. This method exhibits good functional group tolerance and has a broad substrate scope. With the conjugated aldehydes, the one-step synthesis of γ,δ-unsaturated ketones was realized through this reaction. It is noteworthy that the length of the Rh-P bond is an important factor affecting catalytic reactions. The comparative analysis of the crystal structures of axially alkylphosphane and arylphosphane ligated dirhodium(ii) acetate revealed that the shorter Rh-P bond length favors the isomerization process as compared to the longer one. In addition, the dirhodium(ii) compound can be recovered after the completion of the reaction.
Method for preparing intermediate aryl alkyl ketone of hydroxy-ketone photoinitiator
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Paragraph 0020, (2018/07/30)
The invention relates to a method for preparing an intermediate aryl alkyl ketone of a hydroxy-ketone photoinitiator and particularly relates to a method for preparing (substituted) phenyl alkyl ketone. According to the method, the product is separated during reaction, the process is simple, and the production cycle is shortened; a catalyst and a solvent are easily and circularly applied mechanically; the product yield is high, and the production cost is low; and the entire reaction process is environmentally friendly.
A new amino ketone photoinitiator and in UV - LED light curing system application (by machine translation)
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Paragraph 0071; 0072, (2017/08/25)
The invention provides a method suitable for UV - LED light source setting new amino ketone photo initiator, can in long wave zone (365 - 395 nm) has stronger absorption, UV - LED light source is suitable for curing, has overcome the traditional cured high energy consumption, pollution and shortcomings. Electronic unlocalized is good, with strong intramolecular electron transfer performance and excellent photoelectric nature, in the long-wave region 365 nm - 395 nm range have strong absorption, is suitable for high-power UVLED ultraviolet light curing system, compared with the prior art such optical initiator has a considerable advantage. (by machine translation)
