Head-to-Tail Selective [2 + 2 + 2] Cycloadditions of Bisallenes Enabled by Ligand-Free Nickel(0)

IF 13.1 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-08-15 DOI:10.1021/acscatal.5c04046

Stuart C. D. Kennington, Mou Mandal, Roger Monreal-Corona, Arijit Saha, Albert Poater, Anna Roglans* and Anna Pla-Quintana*,

引用次数: 0

Abstract

A ligand-free Ni(0) catalyst enables highly chemo- and regioselective [2 + 2 + 2] cycloadditions between 1,5-bisallenes and acetylenes, affording 6,6-fused hexahydroisoquinoline frameworks under mild conditions. DFT studies reveal that head-to-tail selectivity arises from competing oxidative cyclization pathways with metallacycle geometry dictating product formation. This work highlights how simple nickel complexes can achieve precise molecular construction without the need for ancillary ligands.

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无配体镍催化双烯从头到尾选择性[2 + 2 + 2]环加成

无配体Ni(0)催化剂使1,5-二烯和乙炔之间具有高度的化学和区域选择性[2 + 2 + 2]环加成，在温和条件下形成6,6-融合的六氢异喹啉框架。DFT研究表明，头部到尾部的选择性产生于与金属环几何形状决定产物形成的氧化环化途径的竞争。这项工作强调了简单的镍配合物如何在不需要辅助配体的情况下实现精确的分子结构。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.