1997 Fiscal Year Annual Research Report

新規な触媒を用いる効率的なグリコシル化反応の開発

Research Project

Project/Area Number	08454231
Research Institution	Science University of Tokyo
Principal Investigator	向山光昭東京理科大学, 理学部, 教授 (60016003)
Keywords	グリコシル化反応 / グリコシド / ガラクトース / 2-デオキシグルコース / 2-デオキシリボース / ヌクレオシド
Research Abstract	最近、糖質を含む生物活性物質が次々に単離、構造決定され、その顕著な生理活性が注目を集めている。これらの化合物の多くは糖とアグリコン部分が酸素原子を介して結合しているいわゆるグリコシドとして存在しており、その化学合成の手段としては糖とアグリコン部分を直接結合させるいわゆるグリコシル化反応が一般的であり、これを効率的に実現するための手法を開発することが鍵を握る大切な課題とされている。特に、糖の1位の不斉炭素に由来する二つのジアステレオマ-(1,2-トランス体と1,2-シス体)の選択的合成、すなわち、望みのジアステレオマ-を高立体選択的に作り分けることのできるグリコシル化反応の開発が強く望まれている。昨年度見い出した遊離のリボースを用いる立体選択的グリコシル化反応を本年度はピラノース類のグリコシル化反応に適用し、触媒量のルイス酸を用いて1位に特に脱離基を持たない遊離のガラクトースあるいは2-デオキシグルコースと遊離のアルコールから一挙にグリコシルドを得ることのできる新しい手法を確立することができた。 1-アミノリボシド類のα体およびβ体の立体選択的合成は糖質化学における最重要課題の一つである。本年度の研究においてこの課題に取り組み、炭素3位上の酸素官能基としてチオカルバモイル基を有する2-デオキシリボース誘導体と核酸塩基とのグリコシル化反応をルイス酸触媒の存在下で行うことにより、高い立体選択性をもってβ-リボヌクレオシドを与える優れた手法を見い出すことができた。さらに、炭素5位上の酸素官能基としてチオカルバモイル基を導入することによって、高い立体選択性でα-リボヌクレオシドを得る手法を併せて開発することができた。

Research Products

(11 results)

All Other

All Publications (11 results)

[Publications] Hiromi Uchiro: "Trityl Salt Catalyzed Stereoselective Glycosylation of Alcohols with 1-Hydroxylribofuranose" Chemistry Letters. 79-80 (1996)
[Publications] Teruaki Mukaiyama: "Catalytic Stereoselective Synthesis of Pyrimidine 2-Deoxyribonucleosides" Chemistry Letters. 99-100 (1996)
[Publications] Hiromi Uchiro: "A Significant Effect of a Lithium Salt in the Stereocontrolled Synthesis of α-D-Ribofuranosides" Chemistry Letters. 271-272 (1996)
[Publications] Teruaki Mukaiyama: "A New Efficient Method for Stereoselective Synthesis of 2-Deoxy-C-ribofuranosides" Chemistry Letters. 629-630 (1996)
[Publications] Teruaki Mukaiyama: "An Efficient Method for Catalytic Stereoselective Syuthesis of α-L-Fucopyrauosides" Chemistry Letters. 1123-1124 (1996)
[Publications] Hiromi Uchiro: "A Convenient Method for the Preparation of Disaccharides by Transglycosylation of Methyl Glycosides" Israel Journal of Chemistry. 37. 87-96 (1997)
[Publications] Hiromi Uchiro: "An Efficient Method for Catalytic and Stereoselective Glycosylation with Thioglycosides Promoted by Trityl Tetrakis (pentafluorophenyl) borate and Sodium Periodate" Chemistry Letters. 121-122 (1997)
[Publications] Teruaki Mukaiyama: "Highly Stereoselective Synthesis of 2'-Deoxy-α-ribonucleosides and 2-Deoxy-α-C-ribofuranosides by Remote Stereocontrolled Glycosylation" Chemistry Letters. 389-390 (1997)
[Publications] Teruaki Mukaiyama: "Catalytic Stereoselective Synthesis of α-D-Galactopyranosides from 2,3,4,6-Tetra-O-benzyl-D-galactopyranose and Several Alcoholic Nucleophiles" Chemistry Letters. 403-404 (1997)
[Publications] Teruaki Mukaiyama: "Highly Stereoselective Preparation of α-Glucosides Utilizing Anomerization Reaction with MgBr_2・OEt_2 and a Catalytic Amount of Titanium (IV) tetrahalides" Chemistry Letters. 625-626 (1997)
[Publications] Kazuya Takeuchi: "An Efficient Method for Catalytic and Stereoselective Synthesis of 2-Deoxy-α-D-glucopyranosides from 3,4,6-Tri-O-benzyl-2-deoxy-D-glucopyranose and Several Alcoholic Nucleophiles" Chemistry Letters. 969-970 (1997)

1997 Fiscal Year Annual Research Report

新規な触媒を用いる効率的なグリコシル化反応の開発

Principal Investigator

向山 光昭 東京理科大学, 理学部, 教授 (60016003)

Research Products

[Publications] Hiromi Uchiro: "Trityl Salt Catalyzed Stereoselective Glycosylation of Alcohols with 1-Hydroxylribofuranose" Chemistry Letters. 79-80 (1996)

[Publications] Teruaki Mukaiyama: "Catalytic Stereoselective Synthesis of Pyrimidine 2-Deoxyribonucleosides" Chemistry Letters. 99-100 (1996)

[Publications] Hiromi Uchiro: "A Significant Effect of a Lithium Salt in the Stereocontrolled Synthesis of α-D-Ribofuranosides" Chemistry Letters. 271-272 (1996)

[Publications] Teruaki Mukaiyama: "A New Efficient Method for Stereoselective Synthesis of 2-Deoxy-C-ribofuranosides" Chemistry Letters. 629-630 (1996)

[Publications] Teruaki Mukaiyama: "An Efficient Method for Catalytic Stereoselective Syuthesis of α-L-Fucopyrauosides" Chemistry Letters. 1123-1124 (1996)

[Publications] Hiromi Uchiro: "A Convenient Method for the Preparation of Disaccharides by Transglycosylation of Methyl Glycosides" Israel Journal of Chemistry. 37. 87-96 (1997)

[Publications] Hiromi Uchiro: "An Efficient Method for Catalytic and Stereoselective Glycosylation with Thioglycosides Promoted by Trityl Tetrakis (pentafluorophenyl) borate and Sodium Periodate" Chemistry Letters. 121-122 (1997)

[Publications] Teruaki Mukaiyama: "Highly Stereoselective Synthesis of 2'-Deoxy-α-ribonucleosides and 2-Deoxy-α-C-ribofuranosides by Remote Stereocontrolled Glycosylation" Chemistry Letters. 389-390 (1997)

[Publications] Teruaki Mukaiyama: "Catalytic Stereoselective Synthesis of α-D-Galactopyranosides from 2,3,4,6-Tetra-O-benzyl-D-galactopyranose and Several Alcoholic Nucleophiles" Chemistry Letters. 403-404 (1997)

[Publications] Teruaki Mukaiyama: "Highly Stereoselective Preparation of α-Glucosides Utilizing Anomerization Reaction with MgBr_2・OEt_2 and a Catalytic Amount of Titanium (IV) tetrahalides" Chemistry Letters. 625-626 (1997)

[Publications] Kazuya Takeuchi: "An Efficient Method for Catalytic and Stereoselective Synthesis of 2-Deoxy-α-D-glucopyranosides from 3,4,6-Tri-O-benzyl-2-deoxy-D-glucopyranose and Several Alcoholic Nucleophiles" Chemistry Letters. 969-970 (1997)

向山光昭東京理科大学, 理学部, 教授 (60016003)