Preparation of Novel Chiral Ligands from Natural Sugars and Their Application to Catalytic Asymmetric Synthesis

天然糖类新型手性配体的制备及其在催化不对称合成中的应用

基本信息

批准号：
12839009
负责人：
OHE Kouichi
金额：
$ 2.37万
依托单位：
KYOTO 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 2001
项目状态：
已结题

项目摘要

We developed the highly enantioselective hydrogenation of dehydroamino acids or imines using novel water-soluble chiral rhodium and iridium catalysts bearing hydrophilic phosphine-phosphinite or diphosphinite ligand derived from α,α-trehalose.(1) Preparation of Water-soluble Chiral Rhodium Catalyst having Phosphine-phosphinite LigandMesylation of 2,3:4,6-di-ο-isopropylidene-α-D-glucopyranosyl-(1,1)-4,6-ο-isopropylidene-α-D-gluco-pyranoside (1) derived from α,α-trehalose with MsCl gave 2,3-di-ο-mesyl disaccharide 2. The treatment of 2 with NaOEt gave 2,3-anhydro disaccharide 3. The ring-opening of an epoxide moiety in 3 with KPPh_2 afforded 3-hydroxy-2-diphenylphosphino derivative 4. The reaction of 4 with Ph_2PCl gave 2,3:4,6-di-ο-isopropylidene-α-D-glcopyranosyl-(1,1)-4,6-ο-isopropylidener-2-(diphenyphosphi-no)-2-deoxy-3 -0-(diphenyl- phosphino)-α-D-altropyranoside (5). Finally, the reaction of 5 with [Rh(acac)(cod)] followed by treatment with aqueous HBF_4 afforded a cationic rhodium … More complex 6 bearing six free hydroxyl groups.(2) Preparation of Water-soluble Chiral Iridium Catalyst having Diphosphinite LigandReaction of 1 with Ph_2PCl gave 2,3:4,6-di-ο-isopropylidene-α-D-glcopyranosyl-(1,1)-4,6-ο-isopropylidene-2,3-di-ο-(phenyphosphino)-α-D-altropyranoside (7). The reaction of 7 with [Ir(acac)(cod)] followed by treatment with aqueous HBF_4 afforded a cationic iridium complex 8 bearing six free hydroxyl groups.(3) Asymmetric Hydrogenation of Dehydroamino Acids and their Esters with 6 in an Aqueous MediumThe title complex 6 was found to be an effective catalyst for enantioselective hydrogenation of dehydroamino acids and their esters leading to (R)-α-amino acid derivatives in water or an aqueous/organic biphasic medium. In the biphasic system, the catalyst is immobilized in the aqueous phase. Therefore, the aqueopus phase involving catalyst can be recovered by simple phase separation and reused for further operation in hydrogenation to give almost same level of enantiomeric excess of a hydrogenated product.(4) Asymmetric Hydrogenation of Imines with 8The title complex 8 can act as a catalyst for enantioselective hydrogenation of several imines to give enantiomericaly enriched secondery amines. Less

我们使用新型的水溶性手性犀牛和含有亲水性磷酸磷酸磷脂或二磷酸化的脂肪型催化剂的新型水溶质性手性犀牛和咪定催化剂开发了高度对象选择性的氢化，或者开发了脱氢氨基酸或咪定的催化剂催化剂。 2,3：4,6-二 - 异丙基丙基 - α-d-丙吡喃糖基 - （1,1）-4,6-opropylidene-α-D-α-D-葡萄糖苷（1）衍生自α，α-三链甲酰s的α，α-三链甲酶对2,3-di-di-di-di-di-di-di-befored进行了2,3-di-di-of of Charties contriide contryaive。 2,3-氨基二糖3。用kpph_2在3中的环氧化物部分开环的环，提供3-羟基-2-二苯基磷酸衍生物4。4与pH_2pcl的反应给出了2,3：4,6-Di-opropylidene-α-d-d-d-glcopyranosyl-（1,1）-4,6-ο-异丙基丙基二烯-2-（二苯基磷酸）-α-D-d-altropopyropyaranoside（5）。最后，5与[RH（ACAC）（COD）]的反应，然后用HBF_4水进行处理，提供了阳离子阳极……更复杂的6携带6个游离羟基。（2）水溶性羟基甲状腺催脂催化剂的制备，具有双磷酸磷酸化的连接疗法，该催化剂具有pH_2ppcl的1次磷酸磷酸含量。 2,3：4,6-Di-opropylidene-α-d-d-d-glcopyranosyl-（1,1）-4,6-ο-异丙基二烯-2,3-DI-O-（苯基磷酸）-α-D-d-artropypyropyropyaranoside（7）。 The reaction of 7 with [Ir(acac)(cod)] followed by treatment with aqueous HBF_4 afforded a cationic iridium complex 8 bearing six free hydroxyl groups.(3) Asymmetric Hydrogenation of Dehydromino Acids and their Esters with 6 in an Aqueous MediumThe title complex 6 was found to be an effective catalyst for enantioselective hydrogenation of dehydromino acids and their esters leading to （R）在水或水/有机双相培养基中的α-氨基酸衍生物。在双相系统中，将催化剂固定在水相中。因此，可以通过简单的相分离来恢复涉及催化剂的水相，并重复使用以在氢化中进一步运行，从而使几乎相同水平的对映体的氢化产物过量过量。（4）在8个标题复合物8的非对称氢化能够使甲壳化的催化剂具有多种含有的仿生型，从而使多种含有多种含量的催化剂可为依赖的含量添加促进剂。