- Side-chain oxidation of benzyltrimethylsilanes by iodosylbenzene in the presence of iron and manganese porphyrins
-
Benzyltrimethylsilanes react with iodosylbenzene in the presence of either iron(III) or magnanese(III) tetrakis(pentafluorophenyl)porphyrin (TFPPM, with M = Fe, Mn) to give α-hydroxybenzyltrimethylsilanes, which are then rapidly converted into the corresponding benzaldehydes in the reaction medium. In these reactions the active species is the metal-oxo complex. TFPPM(V) = O, formed by iodosylbenzene and TFPPM. A relative reactivity study for a series of ring substituted benzyltrimethylsilanes has shown that when M = Fe, the reaction is quite selective (ρ = -1.85), with the m-MeO substituent exhibiting a much higher reactivity than expected. When M = Mn, a lower ρ value (-1.15) is observed and no anomalous reactivity is found with the m-MeO group. These result suggest that the side-chain hydroxylation of benzyltrimethylsilane by TFPPMn(V) = O occurs by the well known hydrogen atom transfer mechanism. For the corresponding reactions induced by TFPPFe(V) = O a coupled proton/electron transfer mechanism, which might involve the formation of a charge-transfer complex, seems more likely.
- Baciocchi,Lanzalunga
-
-
Read Online
- Oxidation of alcohols to aldehydes with bromoisobutyrate and dimethyl sulfoxide
-
We have developed an efficient oxidation of primary alcohols to aldehydes with ethyl bromoisobutyrate and dimethyl sulfoxide. Diaryl ketone can also be prepared under this reaction system.
- Wu, Fei-Yue,Chen, Xiao-Hui,Zhou, Hai-Mei,Li, Jia-Qin,Cui, Hai-Lei
-
supporting information
(2021/09/29)
-
- Preparation method of 5, 7-dichloro-1, 2, 3, 4-tetrahydroisoquinoline
-
The invention provides a preparation method of 5, 7-dichloro-1, 2, 3, 4-tetrahydroisoquinoline. The preparation method comprises the following steps: preparing a compound A by taking 3, 5-dichlorobenzoic acid as a raw material; preparing a compound B from the compound A; preparing a compound C from the compound B; preparing a compound D from the compound C; and obtaining a white solid 5, 7-dichloro-1, 2, 3, 4-tetrahydroisoquinoline from the compound D. The preparation method of 5, 7-dichloro-1, 2, 3, 4-tetrahydroisoquinoline provided by the invention has the advantages of high product purity and high product yield.
- -
-
Paragraph 0019; 0021; 0026; 0030-0031; 0039; 0042-0043
(2021/02/06)
-
- Method of continuously oxidizing 3,5-dichlorotoluene for producing 3,5-dichlorobenzaldehyde
-
The invention provides a method of continuously oxidizing 3,5-dichlorotoluene for producing 3,5-dichlorobenzaldehyde and belongs to the technical field of organic synthesis process. In the method, 3,5-dichlorobenzaldehyde is used as a raw material, one or more metal ionic complexes of cobalt, molybdenum, bromine serve as a catalyst, H2O2 serves as an oxidant and acetic acid serves as a solvent, and then the 3,5-dichlorotoluene is continuously oxidized in a tubular reactor to prepare the 3,5-dichlorobenzaldehyde. The method has mild conditions, short reaction time and high raw material utilization rate, can achieve effective control during the reaction process, is safe and stable, allows continuous operation and has high production efficiency.
- -
-
Paragraph 0029-0052
(2017/08/28)
-
- Silver-Mediated Oxidative Trifluoromethylation of Alcohols to Alkyl Trifluoromethyl Ethers
-
The development of an efficient and practical method for the preparation of alkyl trifluoromethyl ethers is urgently demanding. The silver-mediated oxidative O-trifluoromethylation of primary, secondary, and tertiary alcohols with TMSCF3 under mild reaction conditions is established to provide a novel approach to a broad range of alkyl trifluoromethyl ethers. Further, this method is applied to the late-stage O-trifluoromethylation of complex natural products and prescribed pharmaceutical agents.
- Liu, Jian-Bo,Xu, Xiu-Hua,Qing, Feng-Ling
-
supporting information
p. 5048 - 5051
(2015/11/03)
-
- Aromatic-amide-derived olefins as a springboard: Isomerization-initiated palladium-catalyzed hydrogenation of olefins and reductive decarbonylation of acyl chlorides with hydrosilane
-
A highly efficient catalytic protocol for the isomerization of substituted amide-derived olefins is presented that successfully uses a hydride palladium catalyst system generated from [PdCl2(PPh3)2] and HSi(OEt)3. The Z to E isomerization was carried out smoothly and resulted in geometrically pure substituted olefins. Apart from the cis-trans isomerization of double bonds, the selective reduction of terminal olefins and activated alkenes was performed with excellent functional group tolerance in the presence of an amide-derived olefin ligand, and the products were obtained in high isolated yields (up to >99 %). Furthermore, the palladium/hydrosilane system was able to promote the reductive decarbonylation of benzoyl chloride when a (Z)-olefin with an aromatic amide moiety was used as a ligand. Copyright
- Bai, Xing-Feng,Xu, Li-Wen,Zheng, Long-Sheng,Jiang, Jian-Xiong,Lai, Guo-Qiao,Shang, Jun-Yan
-
supporting information; experimental part
p. 8174 - 8179
(2012/08/27)
-
- Isoquinoline compound melanocortin receptor ligands and methods of using same
-
The invention relates to melanocortin receptor ligands and methods of using the ligands to alter or regulate the activity of a melanocortin receptor. The invention further relates to tetrahydroisoquinoline aromatic amines that function as melanocortin receptor ligands and as agents for controlling cytokine-regulated physiologic processes and pathologies, and combinatorial libraries thereof.
- -
-
-
- Oxidative cleavage of oximes with peroxymonosulfate ion
-
Peroxymonosulfate ion (oxone) was found to be an efficient oxidant in the conversion of oximes to carbonyl compounds.
- Bose, D. Subhas,Srinivas
-
p. 3835 - 3838
(2007/10/03)
-
- Process for nucleophilic fluoroalkylation of aldehydes
-
Aryl difluoromethyl sulfone adds to alkehydes under phase transfer conditions to give novel substituted alcohols of the general formula wherein R is an aryl, cycloaliphatic, sec- or tert-aliphatic, or heterocyclic group and Ar is an aryl group. The substituted alcohols of formula I are of particular utility as intermediates in the synthesis of a variety of useful end products. For example, the products of formula I may be utilized in desulfonylation reactions, oxidation reactions and fluorination reactions.
- -
-
-