DEVELOPMENT OF USEFUL REACTIONS USING THE NOVEL LEAVING GROUP, MONOCHLATE

使用新颖的离去基团单甲酸盐开发有用的反应

• 批准号: 10672015
• 负责人: SHIMIZU Takeshi
• 金额: $ 2.11万
• 依托单位: RIKEN (The Institute of Physical and Chemical Research)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10672015/
• 关键词: rearrangement-ring expansion of cyclic ether; chloromethanesulfonate; monochlate; invertion of secondary alcohol; rearrangement of carbon-carbon bond; azide; carbon-nitrogen bond formation; nitrile; テトラヒドロピラン; 炭素-炭素結合形成反応; 環状エーテルの転位-環拡大反応; オキセパ

One of the important and most widely studied organic reactions is nucleophilic substitution at a saturated carbon. Although sulfonates are the most common leaving groups, we sometimes encounter problems such as low reactivity of the methanesulfonates (mesylates; Ms=CHィイD23ィエD2SOィイD22ィエD2-) and instability of the trifluoromethanesulfonates (triflates; Tf=CFィイD23ィエD2SOィイD22ィエD2-). We have found that chloromethanesulfonates (monochlate; Mc=C1CHィイD22ィエD2SOィイD22ィエD2-) served as an extremely efficient leaving group, which exceeds the corresponding mesylates and triflates. Inversion of a wide range of secondary alcohols using the monochlates with cesium acetate in the presence of 18-crown-6 in benzene under reflux has been performed to give the acetates with complete inversion of the configuration in high yields. We have examined further studies on the monochlate as the new and efficient leaving group and found several efficient reactions using monochlates; i.e., (1) rearrangement of the carbon-carbon bond, (2) conversion of secondary alcohols into azides with inversion of the configuration, and (3) conversion of a β-alkoxy primary alcohol into a nitrile.

一个重要的和最广泛研究的有机反应是在饱和碳上的亲核取代。虽然磺酸盐是最常见的离去基团，但我们有时会遇到一些问题，如甲磺酸盐（甲磺酸盐；Ms=CH′′′D23′′r2so′′D22′rd2 -）的反应性较低，以及三氟甲磺酸盐（三氟甲磺酸盐；Tf=CF′r23′r2so′r22′rd2 -）的不稳定性。我们发现chloromethanesulfonates (monochlate; Mc = C1CHィイD22摊位ィエD2SOィイD22摊位ィエD2 -)担任极其高效的离去基团,这超过了相应的甲磺酸和triflates。在苯中有18-冠-6存在的情况下，用单酸盐与醋酸铯在回流条件下对多种仲醇进行了转化，得到了构型完全转化的醋酸盐，产率高。我们对单酸盐作为新的高效离去基的进一步研究进行了考察，发现了几个使用单酸盐的高效反应；即：(1)碳-碳键的重排，(2)仲醇在构型反转的情况下转化为叠氮化物，以及(3)β-烷氧基伯醇转化为腈。

项目成果

Hori, N.: "WFS1 gene mutation search in depressive patients : Detection of 5 missense polymorphisms but no association with depression or bipolar affective disorder"Tetrahedron Lett.. 40. 2145-2148 (1999)

Hori, N.：“抑郁症患者的 WFS1 基因突变搜索：检测 5 个错义多态性，但与抑郁症或双相情感障碍无关”Tetrahedron Lett.. 40. 2145-2148 (1999)

Hori: "Effieiest Synthesis of 2, 3-trans-Tetrahydrofuranes and Oxepanes:Rearrangement-Ring Expansion of Cyclic Ethers Having a Chloromethanesulfonate" Tetrahedron Lett.40(in press). (1999)

Hori：“2, 3-反式四氢呋喃和氧杂环己烷的最有效合成：具有氯甲磺酸酯的环醚的重排环扩展”Tetrahedron Lett.40（出版中）。

Hiranuma, S., Shimizu, T., Nakata, T., Kajimoto, T. Wong, C.-H.: "Synthesis and Inhibition Analysis of Five-Membered Homoazasugars from D-Arabinofuractose via an S N2 Reaction of the Chloremethylsulfonate"Tetrahedron lett.. 36. 8274-8250 (1995)

Hiranuma, S.、Shimizu, T.、Nakata, T.、Kajimoto, T. Wong, C.-H.：“通过氯甲基磺酸盐的 S N2 反应从 D-阿拉伯呋乳糖合成五元同氮糖并进行抑制分析”

Hori, N., Nagasawa, K., Shimizu, T., nakata, T.: "Efficient Synthesis of 2,3-trans-Tetrahydropyranes and Oxepanes: Rearrangement-Ring Expansion of Cyclic Ether Having a Chloromethanesulfonate"Tetrahedron Lett.. 40. 2145-2148 (1999)

Hori, N.、Nagasawa, K.、Shimizu, T.、nakata, T.：“2,3-反式四氢吡喃和氧杂环己烷的高效合成：具有氯甲磺酸盐的环醚的重排环扩展”四面体快报.. 40

Shimizu, T., Hiranuma, S., Nakata, T.: "Efficient Method for Inversion of Secondary Alcohols by Reaction of Chloromethanesulfonates with Cesium Acetate"Tetrahedron Lett.. 37. 6145-6148 (1996)

Shimizu, T.、Hiranuma, S.、Nakata, T.：“通过氯甲磺酸盐与乙酸铯反应转化仲醇的有效方法”Tetrahedron Lett.. 37. 6145-6148 (1996)