Asymmetric Reactions Catalyzed by Fluorous Chiral Catalysts

含氟手性催化剂催化的不对称反应

• 批准号: 11640548
• 负责人: TAKEUCHI Seiji
• 金额: $ 2.62万
• 依托单位: Niigata College of Pharmacy
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11640548/
• 关键词: fluorous chiral catalyst; fluorous chiral ligand; asymmetric reaction; recycling of chiral ligand; recycling of chiral catalyst; フルオラスキラルBINAP; 不斉Heck反応; 安定フルオラスタグ; 触媒; 不斉合成; 配位子のリサイクル; フルオラス二相系反応; CD検出器付きHPLC

We prepared chiral BINOLs (F_<13>BINOL and F_<17>BINOL), BNAP and ephedrine derivatives which bear long fluorous tags, and also a FiaBINOL derivative the hydroxyl groups of which are (S)-1-phenyl-1-hydroxylethylated (FDHPEB). The BINOLs were easily recovered by using a fluorous reverse phase silica gel (FRP) in a BINOL-Ti complex catalyzed asymmetric addtion reaction of Et2Zn to aldehydes and were reused without further purification to give similar enantioselectivities to the original non-fluorous reaction. The chiral fluorous catalyst in the fluorous phase was reused at least 5 times to give similar enantioselectivities to the original one in a toluene/FC-72 biphasic system. FDHPEB was also reused with the use of the FRP silica gel in SmI2 mediated reductive cleavage of 1-methoxy-1-phenylcyclohexanone followed by an asymmetric protonation by FDHPEB. After separation of the organic product by FRP silica gel, the crude product was analyzed by a chiral column HPLC with CD detector. Only two peaks due to the enantiomers of the product were observed and> the data revealed that the enantioselectivity was much higher (95 % ee) man that'of the sample which was obtained by purification with a preparative TLC (88 % ee). The results demonstrated that racemization occured to some extent during the purification. Thus the fluorous chiral ligands and catalysts are recyclable with the use of the FRP silica gel or in a fluorous/organic biphase system and the easy separation of the organic product allowed us to perform a quick analysis using HPLC with CD detector.

项目成果

Yutaka Nakamura, Seiji Takeuchi: "Enantioselective addition of diethylzinc to aldehydes catalyzed by fluorous β-aminoalcohols"Tetrahedron. 57・26. 5565-5571 (2001)

Yutaka Nakamura、Seiji Takeuchi：“含氟 β-氨基醇催化的二乙基锌对醛的对映选择性加成”Tetrahedron 57・26 (2001)。

Nakamura,Yutaka, Takeuchi,Seiji: "Recyclable Fluorous Chiral Ligands and Catalysts Asymmetric Addition of Diethylzinc to Aromatic Aldehydes Catalyzed by Fluorous BINOL-Ti Complexes"Tetrahedron. 58 (in press). (2002)

Nakamura、Yutaka、Takeuchi、Seiji：“可回收的含氟手性配体和催化剂，含氟联醇-钛配合物催化二乙基锌与芳香醛的不对称加成”四面体。

Yutaka Nakamura, Seiji Takeuchi: "Asymmetric alkylation of aromatic aldehydes with diethylzinc catalyzed by a fluorous BINOL-Ti complex in an organic and fluorous biphase system"Tetrahedron Letters. 41. 57-60 (2000)

Yutaka Nakamura、Seiji Takeuchi：“在有机氟双相系统中，氟 BINOL-Ti 配合物催化芳香醛与二乙基锌的不对称烷基化”四面体快报。

Y.Nakamura,S.Takeuchi,Y.Ohgo and D.P.Curran: "Preparation of a Fluorous Chiral BINOL Derivative and Application to an Asymmetric Protonation Reaction"Tetrahedron. 56・3. 351-356 (2000)

Y. Nakamura、S. Takeuchi、Y. Ohgo 和 D. P. Curran：“含氟手性联醇衍生物的制备及其在不对称质子化反应中的应用”四面体 56・3 (2000)。

Yutaka Nakamura, Seiji Takeuchi: "Enantioselective addition of diethylzinc to aldehydes catalyzed by β-aminoalcohols"Tetrahedron. 57. 5565-5571 (2001)

Yutaka Nakamura、Seiji Takeuchi：“β-氨基醇催化的二乙基锌对醛的对映选择性加成”Tetrahedron 57. 5565-5571 (2001)