Stepwise Chemical Reduction of [4]Cyclo[4]helicenylene: Stereo Transformation and Site-Selective Metal Complexation.

Precision Chemistry Pub Date : 2024-11-01 eCollection Date: 2025-01-27 DOI:10.1021/prechem.4c00064

Zheng Zhou, Yong Yang, Jianwei Liang, Sota Sato, Zhenyi Zhang, Zheng Wei

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Abstract

A highly strained macrocycle comprising four [4]helicene panels, [4]cyclo[4]helicenylene ([4]CH, 1), was synthesized through a one-pot macrocyclization and chemically reduced by alkali metals (Na and K), revealing a four-electron reduction process. The resulting di-, tri-, and tetraanions of compound 1 were isolated and crystallographically characterized by X-ray diffraction. Owing to the four axially chiral bi[4]helicenyl fragments, a reversible stereo transformation of 1 between the (S,R,S,R)- and (S,S,R,R)-configurations was disclosed upon the two-electron uptake, which was rationally understood by theoretical calculations. The (S,S,R,R)-configuration of 1 ^2- was further stabilized in triply reduced and tetra-reduced states, where structural deformation led by charges and metal complexation was observed. This study proposed an approach to alter the configuration of cycloarylenes in addition to thermal treatment.

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来源期刊

Precision Chemistry 精密化学技术-

CiteScore

0.80

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0.00%

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期刊介绍： Chemical research focused on precision enables more controllable predictable and accurate outcomes which in turn drive innovation in measurement science sustainable materials information materials personalized medicines energy environmental science and countless other fields requiring chemical insights.Precision Chemistry provides a unique and highly focused publishing venue for fundamental applied and interdisciplinary research aiming to achieve precision calculation design synthesis manipulation measurement and manufacturing. It is committed to bringing together researchers from across the chemical sciences and the related scientific areas to showcase original research and critical reviews of exceptional quality significance and interest to the broad chemistry and scientific community.