A New Medium for Catalyzed C-C Bond Formation Reactions

催化 C-C 键形成反应的新介质

基本信息

批准号：
14078201
负责人：
MIYAURA Nori
金额：
$ 15.36万
依托单位：
Hokkaido University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research on Priority Areas
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2005
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14078201/
关键词：
Water soluble phoshine ligand Aqueous medium Cross-coupling Polymer supported catalyst Organoboronic acid Asymmetric Michael addition reaction Rhodium catalyst Palladium catalyst 水溶性ホスフィンポリマー担持水溶性ホスフィン配位子

项目摘要

1. Catalytic C-H BorylationDirect C-H borylation of arenes catalyzed by a transition metal complex was studied as an economical protocol for the synthesis of a variety of arylboron compounds. Ir/bipyridine-catalyzed C-H borylation of arenes, heteroarenes, and benzylic positions of alkylarenes by bis(pinacolato)diboron or pinacolborane furnished aryl-, heteroaryl-, and benzylboron compounds.2. Carbon-Carbon Bond Formation via the Rhodium Catalyzed Addition Reactions in aqueous mediumVarious rhodium(I) complexes catalyzed the 1,4-addition of organoboronic acids to a,β-unsaturated carbonyl compounds or the Grignard-type addition to aldehydes in a mixture of an organic solvent and water. The reaction provided a convenient method for the asymmetric carbon-carbon bond formation. The rhodium-catalyzed conjugate addition of arylboronic acids to a,β-unsaturated ketones, esters or amides was carried out in water. A complex between [RhCl(cod)]_2 and 2β -cyclodextrin-[Rh(OH)(cod)]_2 catalyzed the … More reaction efficiently in a single aqueous medium.3. Chiral Bis-phosphoramidites for Asymmetric Rhodium-Catalyzed 1,4-AdditionsA chiral bidentate phosphoramidite (BIPAM) was synthesized from Shibasaki's linked-(R)-BINOL and P(NMe_2)_3 as a new ligand for rhodium(I)-catalyzed asymmetric 1,4-addition of arylboronic acids to a,β-unsaturated carbonyl compounds. The effects of BIPAM and Feringa's monodentate phosphoramidite on the yields and enantioselectivities were investigated. The reaction was significantly accelerated in the presence of a base such as KOH and Et3N, allowing the reaction to be completed at the lower temperatures than 50℃.4. Palladium-Catalyzed Addition Reactions of Organoboron compounds.An enantioselective synthesis of cyclic and acyclic β-aryl ketones and esters via palladium(II)-catalyzed 1,4-addition of Ar-[m] (m=B(OH)_2, BF_3K, Si(OMe)_3, SiF_3, BiAr_2) to α, β-unsaturated ketones or esters is discovered. The enantioselection mechanism and efficiency of a chiraphos ligand for structurally planar α, β-unsaturated ketones are discussed on the basis of the X-ray structure of the catalyst and results of DFT computational studies on the modes of coordination of the substrates to the phenylrhodium(I)/(S,S)-chiraphos intermediate. Less

1。催化C-H BorylationDirect C-H Borylation通过过渡金属复合物催化的竞技场是研究多种芳基硼龙化合物的经济方案。 BIS（Pinacolato）Diboron或Pinacolborane提供的芳基 - 芳族烷基烯烃或甲基硼烷提供芳基 - 杂种，杂芳基 - 和苯甲酰硼龙化合物2。通过在中等变化的阳极（I）配合物中催化的添加反应的碳碳键形成，将有机酸的1,4-成分催化为A，β-不饱和的羰基化合物或grignard-type添加的Aldeydes添加aldehydes，在Aldeydes中添加了有机溶液和水的混合物。该反应为不对称的碳碳键形成提供了方便的方法。在水中，将芳香蛋白催化的共轭物添加到A，β-不饱和酮，酯或酰胺中。 [RhCl（COD）] _ 2和2β-环性糖蛋白 - [RH（OH）（COD）] _ 2之间的复合物在单个水培养基中有效地催化了……更有效地反应。3。用于非对称枢轴催化的1,4-添加的手性双磷酰胺手性手性伴磷光岩（BIPAM）与shibasaki的链接 - （r）-binol和p（nme_2）_3的shibasaki Linked-（r） - binol和p（r） - _3 _3合成，作为rhodimand的新ligrigandium（i）。芳基硼酸至A，β-未饱和羰基化合物。研究了BIPAM和Feringa的单次磷光岩对产量和对映选择性的影响。在存在KOH和ET3N等基碱的存在下，该反应显着加速，使该反应在低于50℃.4的温度下完成。有机体化合物的钯催化的添加反应。通过Palladium（ii）的环状β-芳基酮和环状β-芳基酮和酯的对映选择性合成（II） - 催化1,4-cATALY ar- [m] [m]（m = b（m = b（oh）_2，_2，bf_3k，bf_3k，bf_3k，bf_3k，bf_3k，si（bf_3k，si（si），发现β-不饱和酮或酯。基于催化剂的X射线结构和DFT计算研究结果，讨论了chiraphos配体对结构平面α，β-不饱和酮的对映射机制和效率，并讨论了dft计算研究的结果，以实现基质（i）/（i）/（i）/（s，s）-Chiraphoss-imperiate substrates sodiations of catalys a。较少的