清华大学王泉明团队报道金属催化和有机催化在具有锚定脯氨酸的金属纳米团簇中的整合。相关研究成果发表在2023年5月29日出版的国际学术期刊《美国化学会杂志》。

手性金属纳米团簇最近引起了人们的极大关注。通过原子精确的金属纳米团簇实现不对称催化具有挑战性。

该文中，研究人员报道了手性簇合物[Au7Ag8(dppf)3(l-/d-proline)6](BF4)2 (l-/d-Au7Ag8)的合成和总结构测定。超原子团簇l-/d-Au7Ag8在其CD光谱中表现出强烈的镜像Cotton效应。进行密度泛函理论（DFT）计算，以了解对映体对的电子结构和光学活性之间的相关性。令人惊讶的是，脯氨酸在金属纳米簇中的结合可以显著提高不对称Aldol反应的催化效率。与脯氨酸的有机催化相比，Au7Ag8的催化活性的提高归因于金属核和脯氨酸的协同作用，显示了金属催化和有机催化在金属纳米团簇中结合的优势。

附：英文原文

Title: Integration of Metal Catalysis and Organocatalysis in a Metal Nanocluster with Anchored Proline

Author: Jia-Qi Wang, Rui-Lin He, Wen-Di Liu, Qi-Yun Feng, Yan-E Zhang, Chun-Yu Liu, Jing-Xuan Ge, Quan-Ming Wang

Issue&Volume: May 29, 2023

Abstract: Chiral metal nanoclusters have recently been attracting great attention. It is challenging to realize asymmetric catalysis via atomically precise metal nanoclusters. Herein, we report the synthesis and total structure determination of chiral clusters [Au7Ag8(dppf)3(l-/d-proline)6](BF4)2 (l-/d-Au7Ag8). Superatomic clusters l-/d-Au7Ag8 display intense and mirror-image Cotton effects in their CD spectra. Density functional theory (DFT) calculations were carried out to understand the correlation between electronic structures and the optical activity of the enantiomeric pair. Surprisingly, the incorporation of proline in a metal nanocluster can significantly promote the catalytic efficiency in asymmetric Aldol reactions. The increase of catalytic activity of Au7Ag8 in comparison with organocatalysis by proline is attributed to the cooperative effect of the metal core and prolines, showing the advantages of the integration of metal catalysis and organocatalysis in a metal nanocluster.

DOI: 10.1021/jacs.3c02567

Source: https://pubs.acs.org/doi/10.1021/jacs.3c02567