34鈴木 絢子Ayako SUZUKI小池 隆司Takashi KOIKE極限生物の細胞膜を模倣した新しい二分子膜の合成と，膜構造と圧力の相互関係の解析（2018採択）Syntheses of novel bilayer membranes imitated the cell membranes of extremophile, and analysis of correlation between membrane structure and pressure (Project 2018)炭素−水素結合の直接アミノ化を基軸とする面不斉アリールアミン化合物の簡便合成とその応用（2018採択）Development of Simple Synthesis of Planar-chiral Arylamines through Direct C-H Amination(Project 2018)23膜の流動性は細胞の物質透過などの重要な特性を決定しており，近年，圧力変化が膜特性に与える影響を解析することに注目が集まっている．本研究では，膜構造が流動性に与える影響を調査するため，高圧下に生息する古細菌の細胞膜の特徴を模倣し，アルキル長鎖内にポリエーテルを持つ一本鎖型両親媒性化合物の新規合成に成功した．両親媒性化合物は水中で自己組織化し二分子膜を形成する．水中の流動性は，示差走査熱量測定および吸収スペクトル測定により会合状態の変化として評価できる．新規合成化合物のゲル−液晶相転移温度範囲を明らかにするとともに，吸収スペクトルピークの変化波長から，相転移温度以上における会合状態は，H会合とJ会合の中間のオブリーク型であるという知見を得た．The fluidity of membranes determines important properties such as cell permeability. In recent years, there has been much interest in analyzing the effects of pressure changes on membrane properties. In this study, to investigate the effect of membrane structure on the fluidity, we synthesized a new single-chain amphiphilic compound with polyether in the long alkyl chain, mimicking the characteristics of the cell membrane of ar-chaea living under high pressure. The amphiphilic compounds self-assemble in water to bilayers membrane. The fluidity of the amphiphiles in water can be evaluated as a change in the aggregation state by differential scanning calorimetry and absorption spectroscopy. The gel-liquid crystal phase transition temperature range of the newly synthesized compounds were clarified. The change in the wavelength of the absorption spectral peaks indicates that the aggregation state above the phase transition temperature is “the oblique type”, which is between H- and J-aggregation.アリールアミン骨格は医薬品によくみられるだけでなく，優れたレドックスや光学的特性などから機能性有機化合物として注目されている．本研究では穏和な条件下，光触媒的に発生できる窒素中心ラジカル種を用い，アリール炭素−水素結合の直接アミノ化法の開発に挑戦した．その結果，適切に設計されたアミジルピリジニウム塩を用いると芳香環の直接アミド化が可能だった．一方，アミノ化剤によっては光触媒は必ずしも必要ではなく，光照射のみで進行する反応系も見出した．今後，新たな反応系の設計による不斉反応への展開が期待できる知見が得られた．The arylamine skeletons have not been only often found in pharmaceutical products, but also attracted great attention as organic functional materials due to their excellent redox and optical properties. In this study, we have developed a direct amination of aryl C–H bonds using nitrogen-center radical species that can be gener-ated by photocatalysis under mild reaction conditions. As a result, direct amidation of aromatic C-H bonds with well-designed amidylpyridinium salts was realized. On the other hand, depending on the aminating rea-gent, the photocatalyst is not always necessary, and only light irradiation causes the reaction. In the future, development of asymmetric reactions by appropriate design of the reaction system can be expected on the basis of the present results.
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