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由非手性三脚架四齿配体合成金属铑手性配合物：拆分及其在对映选择性狄尔斯-阿尔德反应和1,3-偶极环加成反应中的应用

Synthesis of chiral-at-metal rhodium complexes from achiral tripodal tetradentate ligands: resolution and application to enantioselective Diels-Alder and 1,3-dipolar cycloadditions.

作者信息

Tejero Alvaro G, Carmona María, Rodríguez Ricardo, Viguri Fernando, Lahoz Fernando J, García-Orduña Pilar, Carmona Daniel

机构信息

Departamento de Catálisis y Procesos Catalíticos, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC - Universidad de Zaragoza Pedro Cerbuna 12 50009 Zaragoza Spain

出版信息

RSC Adv. 2022 Dec 2;12(53):34704-34714. doi: 10.1039/d2ra06982b. eCollection 2022 Nov 29.

DOI:10.1039/d2ra06982b
PMID:36545596
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9717581/
Abstract

An improved synthesis of the racemic rhodium compound [RhCl(κ ,,',-L1)] (1) containing an achiral tripodal tetradentate ligand is reported. Their derived solvate complexes [Rh(κ ,,',-L1)(Solv)][SbF] (Solv = NCMe, 2; HO, 3) are resolved into their two enantiomers. Complexes 2 and 3 catalyze the Diels-Alder (DA) reaction between methacrolein and cyclopentadiene and the 1,3-dipolar cycloaddition reaction between methacrolein and the nitrone -benzylidenphenylamine--oxide. When enantiopure ( , )-2 was employed as the catalyst, enantiomeric ratios >99/1, in the at C2 adduct, and up to 94/6, in the 3,5- isomer, were achieved in the DA reaction and in the 1,3-dipolar cycloaddition reaction, respectively. A plausible catalytic cycle that accounts for the origin of the observed enantioselectivity is proposed.

摘要

报道了一种改进的外消旋铑化合物[RhCl(κ ,,',-L1)] (1)的合成方法，该化合物含有一个非手性三脚架四齿配体。其衍生的溶剂化物配合物[Rh(κ ,,',-L1)(Solv)][SbF] (Solv = NCMe, 2; HO, 3)被拆分为其两种对映体。配合物2和3催化甲基丙烯醛与环戊二烯之间的狄尔斯-阿尔德（DA）反应以及甲基丙烯醛与硝酮 -苄叉苯胺-氧化物之间的1,3-偶极环加成反应。当使用对映体纯的( , )-2作为催化剂时，在DA反应和1,3-偶极环加成反应中，分别在C2加合物中实现了对映体比率>99/1，在3,5-异构体中达到了高达94/6。提出了一个合理的催化循环来解释观察到的对映选择性的起源。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c574/9717581/02a4ff107a6e/d2ra06982b-f5.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c574/9717581/af5890f4db6a/d2ra06982b-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c574/9717581/53dfa58154ea/d2ra06982b-f2.jpg
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