光触媒による糖類の位置選択的なC(sp3)-Hアルキル化反応

概要

九州大学学術情報リポジトリ
Kyushu University Institutional Repository

Site-selective C(sp3)–H Alkylation of
Saccharide Derivatives by Photocatalysts
李, 艳茹

https://hdl.handle.net/2324/7157370
出版情報：Kyushu University, 2023, 博士（理学）, 課程博士
バージョン：
権利関係：

（様式３）Form 3

氏

名 ：Li Yanru

Name

論 文 名 ：Site-selective C(sp3)–H Alkylation of Saccharide Derivatives by Photocatalysts
(光触媒による糖類の位置選択的な C(sp3)-H アルキル化反応)
Title
Title

区

分 ：

甲

Category

論 文 内 容 の 要 旨
Thesis Summary
In this thesis, three novel methods for the site-selective C(sp3)–H alkylation of saccharide derivatives
using photocatalysts were developed.
In Chapter 1, I introduced the site-selective alkylation of saccharide derivatives and its potential
applications in various fields. This chapter briefly discussed the different approaches for modifying
saccharides, emphasizing the importance and application of the site-selective C(sp3)–H alkylation of
saccharides.
In Chapter 2, I investigated C(sp3)–H alkylation of 2,3:4,5-bis-O-(1-ethylethylidene)β-D-fructopyranose methyl sulfamate using an iridium photocatalyst under blue LED. This reaction
enables the introduction of various functional groups, such as ester, carbonyl, cyano, and sulfonyl groups, to
the fructopyranose derivative by 1,6-HAT strategy. Furthermore, the N-methyl sulfamate group, acting as a
hydrogen abstractor from the fructopyranose derivative, can be transformed into a hydroxy group.
In Chapter 3, I developed site-selective C(sp3)–H alkylation of saccharides with electron-deficient
alkenes using anthraquinone and tetrabutylammonium decatungstate (TBADT). Interestingly, the reaction
sites can be switched by changing the photocatalysts. Anthraquinone-catalyzed C(sp3)–H alkylation
occurred at C(sp3)–H bond with weak bond dissociation energy (BDE). On the other hand, the
site-selectivity of TBADT-catalyzed C(sp3)–H alkylation was dominated by steric effects. In the
TBADT-catalyzed C(sp3)–H alkylation, the mono-alkylated product was obtained in excellent yield, even
on a gram scale. The reactions were compatible with several electron-deficient alkenes and saccharides, and
provided a variety of C-saccharides.
In Chapter 4, I summarized the results of Chapters 2 and 3. Overall, the results offer promising
methods for the site-selective C(sp3)–H alkylation of saccharides and provide new platforms for the
construction of complex saccharide derivatives. These methods can potentially be used in the synthesis of
new bioactive molecules, which have important applications for drug discovery.

この論文で使われている画像