Article
Chemistry, Multidisciplinary
Simone Ghinato, Federica De Nardi, Paola Bolzoni, Achille Antenucci, Marco Blangetti, Cristina Prandi
Summary: This paper reports a straightforward and efficient method utilizing lithium amide as a metalating agent to promote the metalation/anionic Fries rearrangements of O-aryl carbamates, under aerobic/ambient-friendly reaction conditions. This method enables the sustainable preparation of salicylamide derivatives with high levels of chemoselectivity within ultrafast reaction times, working at room temperature in the presence of air/moisture and using environmentally responsible cyclopentyl methyl ether as a solvent. Furthermore, the regioselective manipulation of O-2-tolyl carbamates has been achieved using interchangeably alkyllithiums or lithium amides, with an unexpected beneficial contribution from the utilization of biorenewable protic eutectic mixtures as non-innocent reaction media.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Geanne M. R. Boston, Holger Butenschon
Summary: In this study, the first syntheses of triflate substituted cobaltocenium cations were reported. The reaction with triflic anhydride yielded the triflate substituted cobaltocenium cations, and further treatment with lithium diisopropylamide led to the first anionic thia-Fries rearrangements of cobaltocenium complexes.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Geanne M. R. Boston, Hendrik M. Philipp, Holger Butenschoen
Summary: Different types of sulfonates undergo distinct rearrangements under comparable reaction conditions, yielding different products and reaction efficiencies. These findings may provide insights for the development of novel organic synthesis reactions.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Geanne M. R. Boston, Irmgard Frank, Holger Butenschon
Summary: Ferrocenyl triflate and 1,1'-ferrocenediyl ditriflate undergo single and double anionic thia-Fries rearrangements at low temperatures, with the latter exclusively forming the meso product. The mechanisms of these rearrangements were studied using DFT calculations, revealing the unprecedented meso diastereoselectivity of the double anionic thia-Fries rearrangement of 1,1'-ferrocenediyl ditriflate.
HELVETICA CHIMICA ACTA
(2021)
Article
Polymer Science
Yuto Ide, Hiroki Ito, Akinori Takasu, Masahiro Higuchi
Summary: In the presence of an aluminum Lewis acid, the anionic chain-growth polymerization of ethyl sorbate was initiated by using common bases, resulting in the formation of cyclic poly(ES) without highly dilute conditions. The ring closure was observed using mass spectroscopy and electron microscope techniques. This method offers a cost-effective alternative to the use of expensive N-heterocyclic carbenes for the synthesis of cyclic vinyl polymers.
JOURNAL OF POLYMER SCIENCE
(2023)
Editorial Material
Chemistry, Multidisciplinary
[Anonymous]
Article
Chemistry, Organic
Subarna Jyoti Kalita, Feng Cheng, Qing-Hua Fan, Norio Shibata, Yi-Yong Huang
Summary: This study presents an exo-selective asymmetric 1,3-dipolar cycloaddition method to access chiral pyrrolidines with four contiguous stereogenic centers, including a fluorinated quaternary stereogenic center at C4. Epimerization promoted by 5.0 equiv of DBU at 90 degrees C results in the formation of chiral 4-fluoropyrrolidines while maintaining the optical purity.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Multidisciplinary Sciences
Satoshi Yamanaka, Yuto Horiuchi, Saya Matsuoka, Kohki Kido, Kohei Nishino, Mayaka Maeno, Norio Shibata, Hidetaka Kosako, Tatsuya Sawasaki
Summary: This article introduces a method based on AirID to identify drug-induced neo-substrates through proximity-dependent biotinylation. The study identifies several new CRBN substrates and demonstrates that this method can serve as a general strategy for studying drug-induced protein-protein interactions in cells.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Hiroto Uno, Koki Kawai, Taichi Araki, Motoo Shiro, Norio Shibata
Summary: Gem-difluoromethylene moieties are attractive in medicinal chemistry due to their ability to mimic other more ubiquitous functional groups. A novel asymmetric method for their construction was developed, allowing easy access to chiral 1,3-dioxanes that contain a tetrasubstituted difluoroalkyl stereogenic center. The gem-difluoro substitution pattern promotes the reaction, and various substrates were suitable for this method.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Kentaro Iwaki, Koki Maruno, Osamu Nagata, Norio Shibata
Summary: The trans-tetrafluoro-lambda 6-sulfanyl (SF4) unit is of medicinal interest due to its high electronegativity, lipophilicity, and unique hypervalent structure. Despite the difficulties in synthesis, the first synthesis of (ethynyl-trans-tetrafluoro-lambda 6-sulfanyl) pyridines and their use as versatile reagents for SF4-alkynylation to carbonyl compounds was reported. The addition reaction of t-ethynyl-SF4-pyridines to carbonyl groups in the presence of MeLi yielded pyridine-SF4-propargylic tertiary and secondary alcohols in high yields.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Kentaro Iwaki, Kazuhiro Tanagawa, Soichiro Mori, Koki Maruno, Yuji Sumii, Osamu Nagata, Norio Shibata
Summary: In this study, we reported a metal-free hydration reaction of pyridine-SF4-alkynes under acidic conditions, which synthesized pyridine-SF4-methyl ketones with yields ranging from 59% to 93%. We further demonstrated the synthetic applications of these compounds, including chlorination, NaBH4 reduction, Baeyer-Villiger oxidation, and the generation of enol triflates. These compounds show promise as useful building blocks in the synthesis of a wide range of SF4-containing drug candidates.
Article
Chemistry, Organic
Jun Zhou, Bingyao Jiang, Zhengyu Zhao, Norio Shibata
Summary: A potassium base-mediated defluoroetherification method for aryl and heteroaryl fluorides is reported, which efficiently and safely provides a wide variety of aryl ethers without the use of metal catalysts, specific ligands, and harsh conditions. This method can also be applied to the late-stage etherification of structurally complex fluorides and bioactive alcohols.
Article
Chemistry, Organic
Yuji Sumii, Hiroto Iwasaki, Yamato Fujihira, Elsayed M. Mahmoud, Hiroaki Adachi, Takumi Kagawa, Dominique Cahard, Norio Shibata
Summary: A protocol for the stereodivergent pentafluoroethylation of N-sulfinylimines has been developed using HFC-125 with KHMDS/triglyme. The presence or absence of triglyme enables the selective synthesis of both diastereomers of the pentafluoroethylated amines. This additive-controlled protocol offers a straightforward and cost-effective alternative to the previously reported base-controlled stereodivergent trifluoromethylation using potassium hexamethyldisilazide (KHMDS) versus P4-tBu.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Masahiro Sugiura, Kazuki Ishikawa, Kota Katayama, Yuji Sumii, Rei Abe-Yoshizumi, Satoshi P. Tsunoda, Yuji Furutani, Norio Shibata, Leonid S. Brown, Hideki Kandori
Summary: This study reports a novel photochemical reaction mediated by a microbial rhodopsin, leading to the selective transition from the all-trans to 7-cis form.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Norio Shibata, Dominique Cahard
Summary: From 2000, our two research groups independently and simultaneously designed and developed a novel family of electrophilic fluorinating reagents based on the use of Cinchona alkaloids. The chiral N-fluoro ammonium salts demonstrated the highest efficiency compared to prior art in enantioselective electrophilic fluorination for a wide range of substrates. In this account, we tell our respective stories, how the same idea germinated in our laboratories, the characterization of the chiral reagents, the use in stoichiometric quantity then the development of a catalytic version, the application to the synthesis of chiral fluorinated molecules of pharmaceutical interest, and finally the exploitation of our reagents by other teams and for other applications.
Review
Chemistry, Multidisciplinary
Yuji Sumii, Norio Shibata
Summary: The trifluoromethyl group is a crucial component in drugs and polymers, making the development of trifluoromethylation reactions a significant area of research in organic chemistry. Various methods, including nucleophilic and electrophilic approaches, transition-metal catalysis, photocatalysis, and electrolytic reactions have been developed over the years. Microflow versions of these reactions have shown great potential for industrial applications due to their scalability, safety, and time efficiency. This review discusses the current state of microflow trifluoromethylation, focusing on different trifluoromethylation reagents and techniques such as continuous flow, flow photochemical, microfluidic electrochemical reactions, and large-scale microflow reactions.
Letter
Chemistry, Organic
Elsayed M. Mahmoud, Soichiro Mori, Yuji Sumii, Norio Shibata
Summary: The synthesis of acyl fluorides from carboxylic acids is achieved using Selectfluor mediated by elemental sulfur. A wide range of acyl fluorides can be accessed while avoiding the formation of acid anhydrides. F-19 NMR spectra indicate that the reactive species in this deoxyfluorination reaction are the in situ generated S-8-fluoro-sulfonium cation A and neutral S-8-difluoride A'.
Article
Multidisciplinary Sciences
Jun Zhou, Zhengyu Zhao, Norio Shibata
Summary: Defluorinative cross-coupling between amines and organic fluorides is achieved via a silylboronate-mediated strategy. This method enables the room-temperature cross-coupling of C-F and N-H bonds, avoiding the high energy barriers associated with thermally induced S(N)2 or S(N)1 amination. The selective activation of the C-F bond of organic fluorides by silylboronate is a significant advantage of this transformation.
NATURE COMMUNICATIONS
(2023)
Editorial Material
Chemistry, Multidisciplinary
Norio Shibata, Dinesh Talwar
Summary: The unique properties and applications of fluorine-containing molecules have had significant impact across different scientific fields, from small to large molecules. This special issue provides a comprehensive overview of the state-of-the-art in fluorine chemistry.
Article
Chemistry, Multidisciplinary
Jun Zhou, Zhengyu Zhao, Bingyao Jiang, Katsuhiro Yamamoto, Yuji Sumii, Norio Shibata
Summary: In this study, an efficient silylboronate-mediated cross-coupling reaction of aryl fluorides with arylalkanes was developed under transition-metal-free, room-temperature conditions. The method showed good adaptability to aryl fluorides with a C(sp(2))-F bond and can be extended to other coupling partners with a C(sp(3))-H bond. It provides a practical and convenient approach to obtain di- and triarylalkanes with tertiary or quaternary carbon centers.
