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Development of Novel Photoelectron Transfer Reaction Systems with Stable Organometallic Compounds Promoted by Acids and Bass

酸和碱促进的稳定有机金属化合物新型光电子转移反应体系的开发

基本信息

批准号：
12640519
负责人：
NISHIGAICHI Yutaka
金额：
$ 2.3万
依托单位：
Shimane University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2000
资助国家：
日本
起止时间：
2000 至 2002
项目状态：
已结题

项目摘要

The effect of basic (nucleophilic) moieties on the activation of organometallic reagents in the photoinduced electron transfer (PET) reaction toward aromatic ketones was investigated. For allyl- and benzyltin reagents, the presence of hydroxyl group at the near position increased the efficiency of the reaction. For allylsilicon reagents, introduction of the 5th ligand into them accelerated the PET reaction efficiently and gave the allylated product in high yields. These reactions also contained the characteristic feature of PET, α-regioselectivity and stereoretention of the double bond in allyl moiety. Similar boron reagents also underwent PET reaction with aromatic ketones by the 4th basic ligand to perform allylation and benzylation. These reactions are the first examples of allylation via PET using silicon and boron reagents. Alkytin reagents, which were not good reagents for PET, could be applied to the carbonyl alkylation by the substitution of an alkyl by a hetero atom. Furthermore, hypervalent (5-coordenated) alkyltin reagents exhibited high efficiency of alkylation.On the other hand, the effect of Lewis acids to the PET reaction was also investigated. Addition of metal salts to ketones accelerated the PET from allylsilicon reagents. As another topic, metal ion inhibited PET from amino moiety in allyltin reagent and selectively promoted PET from allyltin moiety to undergo carbonyl allylation.For comparison with photoreaction, thermal Lewis acid promoted reaction was investigated. Allyltins containing a hydroxyl and an amino group, which were not suitable for the thermal acidic reaction, were successfully applied to the photoallylation reaction. This shows a synthetic merit of the photoreaction. As an advantage of the thermal reaction, Lewis acids could control stereoselectivity in allylation reaction by their coordination mode.

研究了碱性（亲核）基团对有机金属试剂光诱导电子转移（PET）反应的活化作用。对于烯丙基锡和苄基锡试剂，在近位羟基的存在增加了反应的效率。对于烯丙基硅试剂，引入第五配体可有效地加速PET反应，并以高产率得到烯丙基化产物。这些反应还具有PET的特征，即α-区域选择性和烯丙基双键的立体保留。类似的硼试剂也可以通过第4位碱性配体与芳香酮发生PET反应，进行烯丙基化和苄基化。这些反应是使用硅和硼试剂通过PET进行烯丙基化的第一个例子。烷基锡试剂虽然不是PET的好试剂，但可用于杂原子取代烷基的羰基烷基化反应。此外，高价（5-配位）烷基锡试剂具有较高的烷基化效率。另一方面，还研究了刘易斯酸对PET反应的影响。在酮中加入金属盐加速了烯丙基硅试剂的PET反应。另外，金属离子抑制了烯丙基锡试剂中的氨基取代PET，并选择性地促进烯丙基锡取代PET进行羰基烯丙基化反应，并与光催化反应进行了比较，研究了热刘易斯酸促进的反应。含有羟基和氨基的烯丙基锡不适合热酸性反应，但成功地应用于光烯丙基化反应。这显示了光反应的合成优点。刘易斯酸在热反应中的一个优点是可以通过配位方式控制烯丙基化反应的立体选择性。