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ACTIVATION OF METALS AND THEIR UTILIZATION FOR ORGANIC SYNTHESIS

金属的活化及其在有机合成中的应用

基本信息

批准号：
09450342
负责人：
TAKAI Kazuhiko
金额：
$ 8.77万
依托单位：
OKAYAMA UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1999
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09450342/
关键词：
MANGANESE METAL CARBONYL YLIDE CHROMIUM (II)ALKYL RADICAL VITAMIN B12 GEMINAL DICHROMIUM REAGENT ALLYLIC CHROMIUM ALKENYLSILALE 亜鉛マンガンヨウ化アルケニルラジカル 3分子連結反応タンタルイミン錯体 [3+2]環化付加

项目摘要

The following stereoselective organic transformations have developed with an activated manganese matal or chromium (II). (1) Treatment of 1-iodoalkyl triethlsilyl ether, derived from an alkanal and EtィイD23ィエD2SiI in dichloromethane, with a mixture of manganese and PbCIィイD22ィエD2 in THF generates a nonstabilized carbonyl ylide. The ylide reacts with unsaturated compounds, such as α, β-unsaturated esters, allylic ethers, and an aldehyde, to give tetrahydrofuran derivatives (or a dioxolane) via [3+2] cycloadditon reactions. (2) The mild reluctant chromium (II) chloride can discriminate between alkyl iodides, alkyl radicals, and allylic radicals. In the presence of chromium (II) the alkyl radical is so long-lived that it can undergo intermolecular addition to a 1, 3-diene. Rapid one-electron reduction of the formed allylic radical results in an allylic chromium species, which adds to an aldehyde to afford a three-component coupling product. (3) Treatment of α-chloroalkylboronic esters with CrCIィイD22ィエD2 in the presence of LiI and TMEDA generates α-boryl radicals, which add to α, β-unsaturated esters in a 1, 4-fashion under mild conditions in excellent yields. (4) A chromium hydride equivalent generated from CrCIィイD22ィエD2, BィイD212ィエD2, and water reacts regioselectively with 1, 3-dienes to give allylic chromium reagents, and the reagents add to carbonyl compounds in a chemo- and stereoselective manner. (5) A catalytic cycle of a chromium salt in a stereoselective transformation of aldehydes to (E)-1-iodoalknens using a geminal dichromium reagent, is assembled with zinc, MeィイD23ィエD2SiCI, and NaI in dioxane. (6) Iodoform is reduced with manganese in the presence of MeィイD23ィエD2SiCI to give MeィイD23ィエD2SiCHIィイD22ィエD2. A one-pot transformation of aldehydes to (E)-1-alkenyltrimethylsilanes is then performed with iodoform, manganese, MeィイD23ィエD2SiCI, and a catalytic amount of chromium(II) chloride in THF via in situ formation of MeィイD23ィエD2SiCHIィイD22ィエD2.

用活性锰材料或铬（II）进行了以下立体选择性有机转化：(1)在二氯甲烷中，用锰和PbCI （II）的混合物处理1-碘烷基三乙基硅醚，生成非稳定羰基酰物。酰基化合物与不饱和化合物如α、β-不饱和酯、烯丙醚和醛反应，通过[3+2]环加成反应生成四氢呋喃衍生物（或二恶烷）。(2)温和不情愿的氯化铬（II）可以区分烷基碘化物、烷基自由基和烯丙基自由基。在铬（II）的存在下，烷基自由基的寿命很长，可以在分子间加成到1,3 -二烯。形成的烯丙基自由基的快速单电子还原得到烯丙基铬，它与醛结合形成三组分偶联产物。(3)治疗α-chloroalkylboronic酯与CrCIィイD22摊位ィエD2的LiI和TMEDA生成α-boryl自由基,增加α,β不饱和酯1,4-fashion在温和条件下的产量。(4)由CrCI、B、D212、D2和水生成的铬氢化物与1,3 -二烯发生区域选择性反应生成烯丙基铬试剂，并以化学和立体选择性的方式加入羰基化合物。(5)铬盐在醛立体选择转化为(E)-1-碘烯的催化循环中，使用双铬试剂，在二氧六烷中与锌、Me （γ γ γ）、Me （γ γ）、D23 （γ）、D2SiCI和NaI组装。(6)碘仿在存在的情况下，用锰还原得到Me D23 D2SiCI D22 D2。一锅法转换醛(E) 1-alkenyltrimethylsilanes然后执行与碘仿、锰、我ィイc15ィエD2SiCI,和催化量的氯化铬(II)在我的四氢呋喃通过原位形成ィイc15ィエD2SiCHIィイD22摊位ィエD2。