Asymmetric Catalysis by Layred Smectites Multi-Modified with Sugars

糖多重修饰的层状蒙皂石的不对称催化

• 批准号: 07651073
• 负责人: SHIMAZU Shogo
• 金额: $ 1.41万
• 依托单位: CHIBA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07651073/
• 关键词: CHITOSAN; RHODIUM COMPLEXES; PHOSPHINES; ASYMMETRIC HYDROGENATION; CATALYSIS; AMINOSUGARS; CITRONELLAL; CHEMOSELECTIVITY; 粘土鉱物; ヘクトライト; イタコン酸

Hectorite-supported rhodium (I) -chitosan complex (Rh-Chito^+/NaHT) was prepared by the intercalation of [Rh (Chito-OP) (COD) ] ^+ (Rh-Chito^+) (Chito-OP=chitosan phosphite) into sodium hectorites (NaHT) in DMF/H_2O.Asymmetric hydrogenation of alpha, beta-unsaturated carboxylates such as itaconates containing various chain lengths of alcohol groups and chemoselective hydrogenation of citronellal were studied on the intercalation compound.1 Characterization : XRD measurement showed that the basal spacing of Rh-Chito^+/NaHT was 2.02nm. The clearance space (d_<001>-0.96nm) of Rh-Chito^+/NaHT was 1.06nm which suggested that 2/1 helical structure of Rh-Chito^+ was formed in the interlayr rather than 8/5 helical structure. TEM and FT-IR measurement confirm the formation of monolayr of the rhodium complex in the interlayr of hectorite.2 Hydrogenation of itaconates and citronellal : The main hydrogenation product for dimethyl itaconates was dimethyl (R) -methylsuccinate. Small amount of dimethyl mesaconate was formed as an isomerization product during the hydrogenation. Catalytic activity remarkably depended on the reaction solvents. In MeOH,the reaction did not proceed. Asymmetric selectivity of the hetrogenized Rh catalyst was higher than that of Rh-Chito^+ (homogeneous complex). Highest selectivity (16.7% e.e (R) ) was obtained when EtOH/DMF (30 : 1) was used as a reaction solvent. Probably the controlled conformation of helical structure in the interlayr contributes the higher asymmetric selectivity for Rh-Chito^+/NaHT.Chemoselectivity was observed for the hydrogenation of citronellal. Rh-Chito^+/NaHT and Rh-Chito+ predominantly hydrogenated C=O group of citronellal. This catalytic behavior is remarkably different from [Rh (PPh_3) _2 (CCD) ] PF_6 which predominantly hydrogenated C=C bond.

蒙脱石负载铑（I）-壳聚糖配合物（Rh-Chito^+/NaHT）是通过[Rh（Chito-OP）（COD）] ^+（Rh-Chito^+）（Chito-OP=壳聚糖亚磷酸酯）在DMF/H_2O中不对称氢化成锂蒙脱石钠（NaHT）。β-研究了含不同链长醇基的不饱和羧酸酯如衣康酸酯和香茅醛的化学选择性氢化，1表征：XRD测量显示Rh-Chito^+/NaHT的基间距为2.02nm。Rh-Chito <001>^+/NaHT的间隙（d_ -0.96nm）为1.06nm，表明Rh-Chito^+在层间形成的是2/1螺旋结构，而不是8/5螺旋结构。TEM和FT-IR测试证实了铑配合物在锂蒙脱石层间形成单层。2衣康酸酯和香茅醛的氢化：衣康酸二甲酯的主要氢化产物是（R）-甲基琥珀酸二甲酯。在氢化过程中形成少量的中康酸二甲酯作为异构化产物。催化剂的活性与反应溶剂有显著的依赖性。在MeOH中，反应不进行。非均相Rh催化剂的不对称选择性高于Rh-Chito^+（均相络合物）。当以乙醇/DMF（30：1）为反应溶剂时，选择性最高（16.7%e.e（R））。可能是由于中间层螺旋结构的可控构象导致了Rh-Chito^+/NaHT的高不对称选择性。Rh-Chito^+/NaHT和Rh-Chito+主要氢化的香茅醛的C=O基团。这种催化行为与[Rh（PPh_3）_2（CCD）] PF_6主要氢化C=C键的催化行为有明显的不同。

项目成果

T.Uematsu, N.Ichikuni, S.Shimazu: "Modification of Layr Compounds for Host-Guest Catalysis" Proceedings of the 1995 International Conference on Ion Exchange. 275-2280 (1995)

T.Uematsu、N.Ichikuni、S.Shimazu：“主客体催化作用的层状化合物的改性”1995 年国际离子交换会议论文集。

S.Shimazu, K.Ro, T.Sento, N.Ichikuni and T.Uematsu: "Asymmetric Hydrogenation of alpha, beta-Unsaturated Carboxylic Acid Esters by Rhodium (I) Phosphine Complexes Supported on Smectites" Journal of Molecular Catalysis A : Chemical. 107. 297-303 (1996)

S.Shimazu、K.Ro、T.Sento、N.Ichikuni 和 T.Uematsu：“蒙脱石支持的铑 (I) 膦配合物对 α, β-不饱和羧酸酯的不对称氢化” 分子催化杂志 A：化学

S.Shimazu: "Asymmetric Hydrogenation of α,β-Unsaturated Carboxylic Acid Esters by Rhodium(1)Phosphine Complexes Supported on Svnectites" Journal of Molewlar Catalysis A:Chemical. 107. 297-303 (1996)

S. Shimazu：“Svnectites 上的铑 (1) 膦配合物对 α,β-不饱和羧酸酯的不对称氢化”，分子催化杂志 A：化学 107. 297-303 (1996)。

築部浩編、島津省吾 分筆: "分子認識化学(5章)" 三共出版, 222 (1997)

月部宏主编、岛津正吾着：《分子识别化学（第5章）》 三共出版社，222（1997）

Shogo Shimazu: "AsymmetricHydrogenation of α,β-Unsaturated Carboxylic Acid Esters by Rhodium(I)-Phosphine Complexes Supported on Smectites" Journal of Molecular Catalysis. (印刷中). (1996)

Shogo Shimazu：“蒙皂石支持的铑 (I)-膦配合物对 α,β-不饱和羧酸酯的不对称氢化”《分子催化》杂志（1996 年）。