著者
周東 智 市川 聡 阿部 洋 松田 彰
出版者
The Society of Synthetic Organic Chemistry, Japan
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.66, no.1, pp.50-60, 2008-01-01 (Released:2010-06-28)
参考文献数
22
被引用文献数
2 4

Despite considerable progress and extensive effort, a general method for highly stereoselective glycosylation particularly for the 1, 2-cis-glycosylation has not yet been developed and therefore is required. The α/β-stereoselectivity in glycosylation can be affected by the steric and stereoelectronic (anomeric) effects around the anomeric center, which depend on the conformation of the glycosyl donor substrates. Therefore, we hypothesized that highly α- and β-selective glycosylation can be realized by employing conformationally restricted substrates. We showed that the α/β-stereoselectivity was significantly increased by the conformational restriction and was completely inverted by changing the substrate conformation from the 4C1-form into the 1C4-form in radical and nucleophilic C-glycosylation reactions as well as in O-glycosylation reactions. The conformational restriction of substrates also effectively facilitates the α- and β-selective radical cyclization reaction at the anomeric position. Using the method, C-glucoside trisphosphates designed as Ca2+-mobilizing agents were successfully synthesized.
著者
周東 智 嶋脇 健
出版者
北海道大学
雑誌
挑戦的萌芽研究
巻号頁・発行日
2011

cADPR(1)Ca2+動員を担うセカンドメッセンジャーであるcADPR(1)は非常に不安定であるので、申請者が先に開発したcADPRの安定等価体である炭素環アナログcADPcR(cADPR,2)をプロトタイプとして、ADPR標的タンパク質同定のためのバイオロジカルツールの創出を目指した。バイオロジカルツールを創出する上での鍵化合物として4"α-アジドcADPcR(3)を設計し、その合成を達成した。さらに、3が望みの生物学的機能を有することを確認した。