Takeshi Hanamoto's research while affiliated with Saga University and other places

... Subsequent iodocyclization afforded the corresponding 4-CF3-3-iodo-2-substituted thiophenes in good to high yields. It is noteworthy that the substrate bearing a triisopropylsilyl group was intact under optimal reaction conditions due to the bulky silyl group hindering the approach of electrophilic iodine [47] (Scheme 10). Other methods to construct thiophene derivatives from β-CF3-1,3-enynes were also reported. ...

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Versatile Fluorine-Containing Building Blocks: β-CF3-1,3-enynes

... Hanamoto and co-workers [17] (Scheme 10) described in 2019 the use of a g-fluoro b-acetoxypropyl sulfonium salt 25 as the precursor of the corresponding (fluoromethyl)vinyl sulfonium salt for the synthesis of CFH 2 cyclopropanes 26 with stabilized carbanions. This process requiredt he use of 1,8-diazabicyclo [5.4.0]undec-7-ene (DBU) for the in situ generation of the reactive vinylsulfonium salt and the corresponding cyclopropanes were obtained in good to high yields. ...

Reference:

Synthesis of Fluoro‐, Monofluoromethyl‐, Difluoromethyl‐, and Trifluoromethyl‐Substituted Three‐Membered Rings

... Moreover, the intense HOOP modes were observed at 794 and 954 cm −1 . These modes have been assigned to the HOOP vibrations of C14H and HC11=C12H (17,18), the intensities of which are the measures for the degree of chromophore distortions (26,27) about C11=C12 and C13=C14. Therefore, the all-trans RSB chromophore is significantly distorted. ...

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Reisomerization of retinal represents a molecular switch mediating Na+ uptake and release by a bacterial sodium-pumping rhodopsin

... Traditional synthetic routes to access terminal α-fluoroalkenes through olefination or alkene functionalization pathways suffer from key drawbacks such as multi-step starting material syntheses, harsh/hazardous reaction conditions, poor regioselectivity, and/or modest scopes (36)(37)(38)(39). Meanwhile, previously reported metalcatalyzed cross-coupling routes to prepare α-fluorostyrenes require air-sensitive starting materials and/or specialized equipment to handle gaseous VDF (40)(41)(42)(43)(44). To design a more streamlined protocol, we employed VDF-Mg2(dobdc) to enable a base-free, defluorinative Suzuki-Miyaura coupling (45) with air-stable (hetero)aryl boronic acids (Fig. 3B), representing a straightforward route to access α-fluorostyrenes. ...

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Handling Fluorinated Gases as Solid Reagents Using Metal–Organic Frameworks

... Recently, Ye and co-workers have extended this approach to the oxo-alkylation of styrenes with alkyl radicals derived from redox-active esters using photoredox-catalysis. 179 Anodic oxidation was employed by Yoshida and co-workers for the functionalization and oxidation of both alkenes and benzylic positions (Scheme 52). Initially focusing on the direct oxidation of the substrate followed by interception of the resulting carbenium ion with DMSO (Scheme 52a), 180,181 the group later showed the potential of forming electrophilic halogens (325) and chalcogens through anodic oxidation (Scheme 52b). 182 Nucleophilic attack of an olefin onto 325, followed by interception of the resulting carbocation with DMSO once more led to the formation of intermediate 326, ...

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Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

...  Réaction d'addition de Michael La première réaction de Michael promue par des phosphines entre des dérivés propiolates de méthyles et des pro-nucléophiles oxygénés a été développée en 2006 par l'équipe de J. Inanaga (Schéma 32). 74 Il est à noter que seules des oléfines (E) ont été obtenues. Cette haute stéréosélectivité provient du mécanisme même de la réaction ( Figure 12). ...

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Développement de nouvelles méthodologies en organocatalyse asymétrique redox par les phosphines

... Regarding the abundant N-atom sources, nucleophilic difunctionalization of alkenes with simple amines without the use of transition metals would be a cornerstone to improve structural diversity of diamine synthesis. This vicinal amination of the carbon-carbon double bond under metal free conditions has been presented with bifunctional nucleophiles in an intramolecular manner to afford N,N-and N,O-heterocyclic systems using alkenyl-sulfonium salts with two adjacent electrophilic centers [29][30][31][32] . However, the intermolecular difunctionalization of alkenes has not been performed by the utilization of two separate external nitrogen nucleophiles via metal-free vicinal heterodiamination. ...

Reference:

Vicinal difunctionalization of carbon–carbon double bond for the platform synthesis of trifluoroalkyl amines

... Hirotaki et al. reported the synthesis of the melatonin analogues 260 via reaction of substituted indoles (259) with aziridine 258 (Scheme 37D) [161]. It was found that the introduction of the Ns (o-Scheme 35. ...

Reference:

Indole-based melatonin analogues: Synthetic approaches and biological activity

... However, HClO 4 -catalyzed glycosylations have been reported to require only 1.2 equiv of donors. 26 Most of the other research have focused on employing functionalized acyloxy leaving groups including glycosyl phthalates, 27,28 glycosyl o-methoxybenzoates, 29 and glycosyl alkynylbenzoates, 30,31 catalyzed by SnCl 3 ClO 4 , 28 Ph 3 PAuOTf, 30,31 PhCCH/AuCl 3 , 32 and TMSOTf. 27,29,33−36 In most of these cases, the glycoside yields are excellent, but catalysts such as TMSOTf or AgOTf are very expensive and moisture-sensitive, or they contaminate the products with metals. ...

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Practical Glucosylations and Mannosylations Using Anomeric Benzoyloxy as a Leaving Group Activated by Sulfonium Ion

... [51] Then, the authors used ar ing-opening reaction of aziridines 113 to synthesize severalb iorelevant difluoromethyl-b-tryptamine analogs, difluoromethylated oxazolidines, and 2-imidazolines. [52] Others publications, dedicated to the formation of trifluoromethyl aziridines, which will be discussed in more detailsi n the next section devoted to CF 3 -aziridines, reported in their scope one example of difluoromethyl aziridine. Eq. (a)). ...

Reference:

Synthesis of Fluoro‐, Monofluoromethyl‐, Difluoromethyl‐, and Trifluoromethyl‐Substituted Three‐Membered Rings