Catalytic Hydroacylatlon using Rhodium Complex

使用铑配合物的催化加氢酰化

• 批准号: 14572007
• 负责人: SUEMUNE Hiroshi
• 金额: $ 2.24万
• 依托单位: Kyushu University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14572007/
• 关键词: Hydroacylation; rhodium complex; catalytic reaction; double chelation; diene; asymmetric reaction; サリチルアルデヒド; タブルキレーション

Intermolecular hydroacylation between salicylaldehyde and 1,4-penta-or 1,5-hexadienes by Rh-catalyst proceeded under mild reaction conditions to give a mixture of iso-and normal-hydroacylated products. In the hydroacylation reaction, chelation of both salicylaldehyde and diene to the Rh-complex play a crucial role. The ratio of iso-and normal-hydroacylated products could be regulated by the addition of salicylic acid or amines. The effects of various Rh-complexes, solvents, and additives were examined, and the plausible mechanisms of the catalytic cycle were proposed on the basis of the basis of the deuterium-labeling salicylaldehyde experiments.

在温和的反应条件下，水杨醛与1，4-五烯或1，5-己二烯在铑催化剂作用下发生分子间氢酰化反应，得到异氢酰化产物和正氢酰化产物。在氢酰化反应中，水杨醛和双烯对铑络合物的螯合作用起着至关重要的作用。异-和正-加氢酰化产物的比例可以通过添加水杨酸或胺来调节。各种铑配合物，溶剂和添加剂的影响进行了检查，并提出了合理的催化循环的机制的基础上的氘标记水杨醛实验的基础上。

项目成果

M.Tanaka, H.Suemune et al.: "Double-Chelation-Assisted Rh-Catalyzed Intermolecular Hydroacylation"Organic Letters. 5. 1365-1367 (2003)

M.Tanaka、H.Suemune 等人：“双螯合辅助 Rh 催化分子间氢酰化”有机快报。

M.Imai, H.Suemune 他7名: "Double-Chelation-Assisted Rh-Catalyzed Intermolecular Hydroacylation between Salicylaldehydes and 1,4-Penta-or 1,5-Hexadienes"Journal of Organic Chemistry. 69. 1144-1150 (2004)

M.Imai、H.Suemune 等 7 人：“水杨醛和 1,4-五-或 1,5-己二烯之间的双螯合辅助 Rh 催化分子间氢酰化”有机化学杂志 69. 1144-1150 (2004) ）

M.Tanaka, K.Sakai, H.Suemune: "Asymmetric Rhodium-catalyzed Intramolecular Hydroacylation for Five-membered Ring Keton Formation"Current Organic Chemistry. 7・4. 353-367 (2003)

M.Tanaka、K.Sakai、H.Suemune：“五元环酮形成的不对称铑催化分子内氢酰化”《现代有机化学》7・4（2003）。

M.Tanaka, H.Suemune 他7名: "Double-Chelation-Assisted Rh-Catalyzed Intermolecular Hydroacylation"Organic Letters. 5. 1365-1367 (2003)

M.Tanaka、H.Suemune 等 7 人：“双螯合辅助 Rh 催化分子间氢酰化”《有机快报》5. 1365-1367 (2003)。

M.Tanaka, K.Sakai, H.Suemune: "Asymmetric Rhodium-catalyzed Intramolecular Hydroacylation for Five-membered Ring Ketone Formation"Current Organic Chemistry. 7・4. 353-367 (2003)

M.Tanaka、K.Sakai、H.Suemune：“五元环酮形成的不对称铑催化分子内氢酰化”《现代有机化学》7・4（2003）。