A5009234502- Fluorine in Organic Chemistry
- Cyclopropane Reaction Mechanisms
- Asymmetric Synthesis and Catalysis
- Chemical Synthesis and Analysis
- Synthesis of β-Lactam Compounds
- Asymmetric Hydrogenation and Catalysis
- X-ray Diffraction in Crystallography
- Synthesis and Catalytic Reactions
- Crystallization and Solubility Studies
- Catalytic C–H Functionalization Methods
- Synthesis and Reactions of Organic Compounds
- Catalytic Cross-Coupling Reactions
- Inorganic Fluorides and Related Compounds
- Carbohydrate Chemistry and Synthesis
- Synthesis and Biological Evaluation
- Synthetic Organic Chemistry Methods
- Computational Drug Discovery Methods
- Advanced Synthetic Organic Chemistry
- Organoboron and organosilicon chemistry
- Peptidase Inhibition and Analysis
- Drug Transport and Resistance Mechanisms
- Antibiotic Resistance in Bacteria
- Cancer therapeutics and mechanisms
- Oxidative Organic Chemistry Reactions
- Sulfur-Based Synthesis Techniques
Setsunan University
2015-2024
University of St Andrews
2024
Municipal Hirakata City Hospital
2015-2018
A highly reactive alkylrhodium complex was formed from Me2Zn and RhCl(PPh3)3 effectively catalyzed a Csp3–Csp3 homocoupling reaction of benzyl halides. coupling using Rh catalyst has not been reported up to now. The proceeded under very mild conditions gave the corresponding products even if they had substituents such as an uncovered formyl or hydroxymethyl group.
Synthesis of α-CF3 carbonyl compounds has been recognized to be difficult up now because the polarization CF3δ−-Iδ+ is opposite that CH3δ+-Iδ−, and this makes it introduce CF3+ unit enolates. We recently reported an effective α-trifluoromethylation ketones by using Et2Zn with Rh catalyst, but mechanism not fully cleared. Now, we carried out detailed mechanistic studies found involvement a highly reactive alkylrhodium complex which derived from RhCl(PPh3)3 in α-trifluoromethylation....
(E)-Trimethyl-(3,3,3-trifluoroprop-1-enyl)silane (1) was synthesized as a reagent for use in Hiyama cross-coupling reactions the production of β-trifluoromethylstyrene derivatives. Cross-coupling 1 with electronically diverse aryl iodides achieved by treatment CsF presence catalytic amounts palladium to afford desired products moderate good yields.
A nickel-catalyzed Negishi coupling of bromodifluoroacetamides with arylzinc reagents has been developed. This reaction allows access to difluoromethylated aromatic compounds containing a variety aryl groups and amide moieties. Furthermore, highly effective transformation the functionalized difluoromethyl group (−CF2CONR1R2) was realized via microwave-assisted reduction under mild conditions. The notable features this strategy are its generality use low-cost nickel catalyst ligand; thus,...
Abstract This account concentrates on our new methodologies for the synthesis of fluorine analogues amino acids and their derivatives using Reformatsky‐type reactions ethyl bromodifluoroacetate dibromofluoroacetate with imines promoted by Wilkinson catalyst. First, we present rhodium‐catalyzed reaction diethylzinc chemoselective α,α‐difluoro‐β‐lactams non‐cyclized products, 3‐alkylamino‐2,2‐difluorocarboxylates. was expanded to asymmetric difluoro‐β‐lactams two types chiral auxiliaries. To...
An enantioselective Reformatsky reaction has been developed for the of ethyl dibromofluoroacetate (1) with an imine. This method represents first ligand-promoted imino-Reformatsky approach to use a halofluoroacetate. The amino alcohol ligand allowed preparation enantioenriched α-bromo-α-fluoro-β-lactams in good yields enantioselectivities up 96% ee. process also provided access β-lactam rings bearing two stereogenic centers.
A new fluorous ligand was synthesized from the acetonide of dimethyl tartarate, which showed excellent asymmetric induction on addition dimethylzinc to aldehydes. This will be useful for synthesis bioactive compounds with a methyl carbinol moiety. It could recycled without using solvent or column.
1,3-Diketones were synthesized from α,β-unsaturated ketones by treatment with acid chlorides and Et2Zn in the presence of RhCl(PPh3)3. This is a very simple extremely chemoselective reaction to give adduct at α-position ketones.
The combination of Et2Zn and RhCl(PPh3)3 led to the facile generation a rhodium-hydride complex (Rh-H) that catalyzed 1,4-reduction α,β-unsaturated esters. resulting rhodium enolate performed as Reformatsky-type reagent reacted with various imines give syn-β-lactams in good excellent yields high diastereoselectivity.
Oxidative Sonogashira cross-coupling reactions of (E)-trimethyl(3,3,3-trifluoroprop-1-enyl)silane with arylacetylene were achieved using silver fluoride and a palladium catalyst, to afford high yields various 1,3-enynes CF3 group on the terminal sp(2) carbon. Silver promoted C-Si bond dissociation oxidation palladium, enabling catalytic use palladium.
A practical and highly enantioselective Reformatsky reaction of ethyl bromodifluoroacetate with imines using a cheap commercially available amino alcohol ligand is described.
The Hiyama cross-coupling reaction of (E)-trimethyl(3,3,3-trifluoroprop-1-enyl)silane (1) with 2-iodoaniline (2) proceeded without any protection the amino group. coordination copper(II) fluoride to 2,2′-bipyridyl provided source required trigger this reaction, affording (E)-2-(3,3,3-trifluoroprop-1-enyl)aniline (3). In presence a stoichiometric amount [Cu(OTf)]2·C6H6, treatment 3 an aryl aldehyde at 200 °C 2-aryl-3-trifluoromethylquinoline (4) via oxidative cyclization in situ-generated...
The high diastereoselective synthesis of chiral difluoro-β-lactams (3) was attained by treatment ethyl bromodifluoroacetate (1), 2-hydroxy-1-phenylethyl group substituted imines (2) and diethylzinc in the presence rhodium-catalyst.The absolute configuration 3 determined X-ray analysis 3,5-dinitrobenzoate (6) derived from 3.Nowadays, fluorinated compounds have received a great interest medicinal chemists due to unique physical biological properties imparted fluorine. 1,2,3A large number...