2,2'-二取代氟化联萘衍生物的合成方法及其作为手性单磷酸催化剂设计中手性源的应用

Synthetic Method for 2,2'-Disubstituted Fluorinated Binaphthyl Derivatives and Application as Chiral Source in Design of Chiral Mono-Phosphoric Acid Catalyst.

作者信息

Momiyama Norie, Okamoto Hiroshi, Shimizu Masahiro, Terada Masahiro

机构信息

Department of Life and Coordination-Complex Molecular Science, Institute for Molecular Science Graduate School of Physical Sciences, Graduate University for Advanced Studies (SOKENDAI), Okazaki Aichi, Japan.

Department of Chemistry, Graduate School of Science, Tohoku University, Sendai, Miyagi, Japan.

出版信息

Chirality. 2015 Aug;27(8):464-75. doi: 10.1002/chir.22429. Epub 2015 Feb 9.

DOI:10.1002/chir.22429

PMID:25665035

Abstract

A practical synthetic method for 2,2'-disubstituted fluorinated binaphthyl derivatives was achieved using magnesium bis(2,2,6,6-tetramethylpiperamide) [Mg(TMP)(2)], prepared from LiTMP (2 equiv) and MgBr(2) (1 equiv), which allows for access to a variety of fluorinated binaphthyl compounds. The utility of the fluorinated binaphthyl backbone was evaluated in F10 BINOL derived chiral mono-phosphoric acid (R)- as the chiral Brønsted acid catalyst. The catalyst (R)- performs exceptionally well in the catalytic enantioselective imino-ene reaction, demonstrating the potential of a fluorinated binaphthyl framework.

摘要

使用由双（2,2,6,6 - 四甲基哌啶酰胺）锂（LiTMP，2当量）和溴化镁（MgBr₂，1当量）制备的双（2,2,6,6 - 四甲基哌啶酰胺）镁[Mg(TMP)₂]，实现了一种实用的合成2,2'-二取代氟化联萘衍生物的方法，该方法可用于制备多种氟化联萘化合物。在F10 BINOL衍生的手性单磷酸（R） - 作为手性布朗斯特酸催化剂中评估了氟化联萘骨架的效用。催化剂（R） - 在催化对映选择性亚氨基 - 烯反应中表现出色，证明了氟化联萘骨架的潜力。