著者
友重 秀介
出版者
公益社団法人 有機合成化学協会
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.77, no.3, pp.264-266, 2019-03-01 (Released:2019-03-07)
参考文献数
9

Bacteria possess a cell wall based on a rigid extracellular matrix comprised of peptidoglycan (PG), which maintains their structural integrity. Although PG is a molecule that has attracted interest from various research fields, such studies have been limited by the difficulty to isolate the desired PG fragments. In order to make PG fragments available, many efforts have been made to achieve their synthesis. This review summarizes the synthetic strategies reported for the construction of PG fragments by the Fukase and Fujimoto’s group as well as the Mobashery’s group. Furthermore, applications of synthetic PG fragments in chemical biology are described.
著者
西川 剛 大内 誠
出版者
公益社団法人 有機合成化学協会
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.81, no.4, pp.313-323, 2023-04-01 (Released:2023-04-08)
参考文献数
59

In chain-growth polymerization, (co)polymerization abilities of monomers are heavily dependent on the element or functional group attaching to vinyl moiety, resulting in the limitation of accessible polymers. The replacement of the element on the polymer main chain could lead to access new class of polymers with overcoming the synthetic limitations. Herein, we describe the usability of alkenylboronic acid derivatives as the monomers for radical polymerization and post-polymerization transformation through carbon-boron bond-cleaving side-chain replacement. The key for radical polymerization ability of alkenyl boronate was vacant p-orbital of boron for moderate stabilization of chain growth radical. The alkenyl boronate monomers are usable for copolymerization with common monomers as well as for RAFT polymerization. The C-B bond transformation allows syntheses of conventionally inaccessible polymers, such as poly(α-methyl vinyl alcohol), poly(α-methyl vinyl amine), styrene-vinyl alcohol copolymer, and ethylene-acrylate copolymer. Boron on the polymer main chain was also used as the trigger for stimuli-responsive backbone degradation of methacrylate polymer through C-B bond homolysis and β-scission. Thus, alkenyl boronate monomers have an impact on not only breakthrough of the limitation in polymer synthesis but also development of novel polymer functions.
著者
西依 隆一
出版者
公益社団法人 有機合成化学協会
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.81, no.7, pp.731-732, 2023-07-01 (Released:2023-07-06)
参考文献数
9

Quantum mechanical tunneling (QMT) is a quantum mechanical phenomenon that enables particles to penetrate potential energy barrier despite a lack of energy to overcome it. It has become clear that how important tunneling is for understanding the rates and selectivities of chemical reactions in the last few years. In this short review, recent examples of hydrogen tunneling reactions are described.
著者
小田木 陽 山中 正浩
出版者
公益社団法人 有機合成化学協会
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.81, no.7, pp.706-717, 2023-07-01 (Released:2023-07-06)
参考文献数
48

Organocatalysis has become widely used since the early 2000s as a third type of catalysis in addition to the two types of catalysis, metals and enzymes, and the Nobel Prize in Chemistry was awarded in 2021 for its pioneering achievements. In organocatalytic reactions, stereoselectivity is often controlled by the cooperative action of weak interactions such as hydrogen bonding and dispersion interactions, and it is extremely difficult to elucidate the stereocontrol mechanism from experimental perspectives. On the other hand, recent advances in computational chemistry have made it possible to deeply understand transition state and clarify important roles in controlling the stereoselectivities in organocatalytic reactions. Furthermore, the findings computationally revealed can provide guidelines for the design of new reactions and catalytic structures. Herein, we describe asymmetric oxidation reactions using conformationally flexible bifunctional guanidine-bisurea organocatalysts developed by us and theoretical analysis of the transition states of these reactions. We also discuss the development of novel catalytic reactions and catalyst designs based on the obtained transition state models.
著者
阿部 匠 山田 康司 西 剛秀
出版者
公益社団法人 有機合成化学協会
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.78, no.6, pp.597-607, 2020-06-01 (Released:2020-06-12)
参考文献数
80
被引用文献数
6 8

C3-Nucleophilic substitution of indoles has been limited because the transformation requires an umpolung of the C3 position of indoles. Among the indole derivatives, indole-2,3-epoxides could be potentially be used as C3-electrophilic reagents due to the electrophilic nature of the C2 and C3 positions. However, their use as C3 electrophilic reagents has not been possible so far due to their instability.We describe a novel and bench stable surrogate of indole-2,3-epoxide, 2-hydroxyindoline-3-triethylammonium bromide (HITAB), which was found to be a convenient reagent for formal C3-electrophilic reactions of indoles with nucleophiles. By taking advantage of the nucleophilic character of the oxygen of the 2-hydroxyindoline, interrupted retro-Claisen and interrupted Feist-Bénary reactions with 1,3-dicarbonyl compounds, one-pot formation of furodiindolines from 3-substituted indoles were achieved. Furthermore, we developed a novel cascade reaction of the indole-2,3-epoxide surrogate with γ-carbolines to access multiheterocyclic compounds containing both isotryptamines and pyrimido[1,6-a]indoles. This reaction utilizes the in situ formation of a bulky quaternary ammonium salt via ammonium exchange, which undergoes Hofmann elimination/vinylogous Mannich/retro-Mannich/cyclization cascade sequences. The synthetic potential of the ammonium salts was demonstrated by the short synthesis of cryptolepine, iheyamine A, racemocine B derivative, and neocryptolepine derivative.
著者
市丸 嘉
出版者
公益社団法人 有機合成化学協会
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.74, no.10, pp.993-994, 2016-10-01 (Released:2016-11-07)
参考文献数
7

Recently, the development of selective and powerful inhibitors for enzymes and receptors by structural basis chemical biology is desired. The development has been made successfully by addition of potential to form covalent-linkage with the target-protein to affinity component. Michael acceptors are a powerful and hopeful function to introduce a potential of the covalent-linkage formation to the anticancer agents. This short review describes several recent examples utilizing the covalent-linkage based on the Michael addition reaction in vivo and a possibility of reversible control of the adduct formation.
著者
浜田 翔平
出版者
公益社団法人 有機合成化学協会
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.78, no.8, pp.813-815, 2020-08-01 (Released:2020-08-06)
参考文献数
10

DNA encoded library (DEL) has emerged as a widely utilized chemical library, possessing DNA-tag on each compound, for discovering hit compounds in drug discovery. However, synthetic methods for DEL are not fully exploited due to the difficulty in chemical transformation of DNA encoded compounds. This mini-review focuses on the recent development on organic synthesis for diversity expansion of DEL.
著者
加藤 南
出版者
公益社団法人 有機合成化学協会
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.77, no.2, pp.185-186, 2019-02-01 (Released:2019-02-08)
参考文献数
8

Two dimensional Covalent Organic Frameworks (2D COFs) are new porous materials synthesized from only organic molecules. The 2D COFs consist of light elements that can form strong covalent bonds. The properties of 2D COFs such as pore size, shape and character are easily controlled. The 2D COFs are expected to be applied for a gas storage, an electrochemical device and so on. This review summarized the characteristics and new synthetic methods of 2D COFs.
著者
山内 泰宏 星本 陽一 生越 專介
出版者
公益社団法人 有機合成化学協会
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.79, no.7, pp.632-641, 2021-07-01 (Released:2021-07-07)
参考文献数
72

Practical methods have been established for the synthesis of multifunctional N-heterocyclic carbenes (NHCs) via the introduction of substituents on either the nitrogen atom(s) or the backbone of the NHCs. However, their use has been mainly limited to acting as multidentate ligands for metal complexes. Herein, results of our recent studies on the synthesis and application of N-phosphine oxide-substituted imidazolylidenes (PoxIms) as novel type of multifunctional NHCs are discussed. PoxIms were used not only as a mono-/bi-dentate ligand for mono-/bi-metallic complexes, but also as an external stimuli-responsive Lewis base for achievement of the frustration revival strategy as well as a reagent for the direct phosphinoylation of CO2 and carbonyl compounds. These results manifest the pioneering role of PoxIms as a multifunctional multipurpose NHC.