Anionic 5-endo-dig cyclizations: an experimental investigation of in-plane aromaticity involving a non-enolate carbanion nucleophile

IF 4.7 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Chemistry Frontiers Pub Date : 2025-08-01 DOI:10.1039/d5qo00547g

Kristina M. Nugent, Silas Q. Hintze, Pradip Maity, Salvatore D Lepore

引用次数: 0

Abstract

Cyclitive additions of aliphatic carbanions to non-electrophilic carbon-carbon triple bonds under mild, transition-metal-free conditions are described for the first time. These results confirm theoretical models that invoke in-plane aromaticity to pre-dict the favorability of 5-endo-dig reactions in these systems. In contrast to related Conia-ene cyclizations (5-enolexo-endo-dig), our results generally led to cyclic and allene products in near parity ratios across a broad range of substrates, suggesting that cyclization may proceed via an early ambimodal transition state. Experimental results are presented with a view to re-fining existing mechanistic models for this growing class of alkyne reactions.

查看原文本刊更多论文

阴离子5-内环化：涉及非烯醇碳离子亲核试剂的面内芳香性的实验研究

在温和、无过渡金属的条件下，首次描述了脂肪族碳离子在非亲电碳-碳三键上的循环加成。这些结果证实了利用面内芳构性来预测这些体系中5端反应的有利性的理论模型。与相关的conni -ene环化（5-烯烯外-内切）相反，我们的研究结果通常会在广泛的底物中产生接近奇偶比的环和烯产物，这表明环化可能通过早期的双峰过渡态进行。本文给出了实验结果，以期对这类不断增长的炔类反应的现有机理模型进行改进。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Organic Chemistry Frontiers CHEMISTRY, ORGANIC-

CiteScore

7.90

自引率

11.10%

发文量

686

审稿时长

1 months

期刊介绍： Organic Chemistry Frontiers is an esteemed journal that publishes high-quality research across the field of organic chemistry. It places a significant emphasis on studies that contribute substantially to the field by introducing new or significantly improved protocols and methodologies. The journal covers a wide array of topics which include, but are not limited to, organic synthesis, the development of synthetic methodologies, catalysis, natural products, functional organic materials, supramolecular and macromolecular chemistry, as well as physical and computational organic chemistry.