The selective electrochemical fluorination of S-alkyl benzothioate and its derivatives

• Shunsuke Kuribayashi,
• Tomoyuki Kurioka,
• Shinsuke Inagi,
• Ho-Jung Lu,
• Biing-Jiun Uang and
• Toshio Fuchigami

Beilstein J. Org. Chem. 2018, 14, 389–396, doi:10.3762/bjoc.14.27

• -fluorination. Based on these findings, we anticipated that the α-cationic intermediate could also be generated anodically from S-alkyl benzothioates. Moreover, we previously successfully carried out an anodic fluorodesulfurization of S-aryl thiobenzoates, and found that the indirect electrolysis using a

Highly selective electrochemical fluorination of dithioacetal derivatives bearing electron-withdrawing substituents at the position α to the sulfur atom using poly(HF) salts

• Bin Yin,
• Shinsuke Inagi and
• Toshio Fuchigami

Beilstein J. Org. Chem. 2015, 11, 85–91, doi:10.3762/bjoc.11.12

• having a strongly electron-withdrawing nitrile group gave the α-fluorination product predominantly regardless of the poly(HF) salts used. Keywords: anodic fluorination; anodic fluorodesulfurization; electrosynthesis; fluorination product selectivity; poly(HF) salt; Introduction The introduction of

• ][17][18][19][20]. More than 20 years ago, we reported the first successful example of the electrochemical selective fluorination of heteroatom-containing compounds such as α-(phenylthio)ester and its analogues as shown in Scheme 1 [21][22]. Furthermore, anodic fluorodesulfurization of dithioacetals

• . Further anodic fluorodesulfurization occurs to provide the corresponding difluorinated products 4b and 4d, respectively. On the other hand, the desulfurization of intermediate D followed by reaction with fluoride provides the corresponding fluorodesulfurization products 3b, 3d, and 3f. When high HF

The Shono-type electroorganic oxidation of unfunctionalised amides. Carbon–carbon bond formation via electrogenerated N-acyliminium ions

• Alan M. Jones and
• Craig E. Banks

Beilstein J. Org. Chem. 2014, 10, 3056–3072, doi:10.3762/bjoc.10.323

• carbohydroxylation reaction and postulated intermediate 18 [18]. A radical addition and electron transfer reaction of N-acyliminium ions generated electrosynthetically [19]. Catalytic indirect anodic fluorodesulfurization reaction [37]. Micromixing effects on yield 92% vs 36% and ratio of alkylation products [43

• radicals from the cation pool method [24][25]. Indirect electrolysis methods The only indirect anodic oxidation method to perform the Shono-oxidation with a thiophenyl electroauxiliary has been reported by Fuchigami and co-workers [36]. Using a catalytic triarylamine redox mediator, anodic

• fluorodesulfurization occurred (Scheme 7). Direct Shono-type fluorination of an α-carbon to an amide has also been reported [37]. Technical advances in the Shono electroxidation reaction The “cation-pool” method for the generation of N-acyliminium ions [17][18][19][20][21][22][23][24][25][26][27][28][29][30][31] has