碳环构筑在药物与功能材料合成中至关重要,炔烃广泛应用于环合反应,但碳环合成仍具挑战。因此,新型炔烃碳环化策略成为研究热点,其中RATC策略为碳环构筑提供了新思路。本文介绍了RATC反应的研究进展,分子内RATC反应如Heiba等多取代环戊...碳环构筑在药物与功能材料合成中至关重要,炔烃广泛应用于环合反应,但碳环合成仍具挑战。因此,新型炔烃碳环化策略成为研究热点,其中RATC策略为碳环构筑提供了新思路。本文介绍了RATC反应的研究进展,分子内RATC反应如Heiba等多取代环戊烷制备、刘心元等6(5)-6-5稠环构建及Studer等1-三氟甲基炔丙基环戊烷合成。随后,文章探讨分子间RATC策略,介绍了李金恒等以1,4-二氧六环为自由基前体的Inter-RATC反应和张国柱等通过Inter-RATC构建环丁烷的反应,尽管存在局限性,但它们为碳环构筑提供了新方法。The construction of carbon rings is crucial in the synthesis of pharmaceuticals and functional materials. Alkynes are widely used in cyclization reactions, yet the synthesis of carbon rings remains challenging. Therefore, novel alkyne carbon cyclization strategies have become a research hotspot, among which the RATC strategy offers new insights into carbon ring construction. This article introduces the research progress of RATC reactions, focusing on intramolecular RATC reactions such as the preparation of multisubstituted cyclopentanes by Heiba et al., the construction of 6(5)-6-5 fused rings by Liu et al. and the synthesis of 1-trifluoromethylallylcyclopentanes by Studer et al. Subsequently, the article explores intermolecular RATC strategies, presenting the Inter-RATC reaction using 1,4-dioxane as a radical precursor by Li et al. and the construction of cyclobutanes through Inter-RATC by Zhang et al. Despite their limitations, these strategies provide novel methods for carbon ring construction.展开更多
A strategy for copper-catalyzed and biphosphine ligand controlled boracarboxylation of 1,3-dienes and CO_(2) with 3,4-selectivity was developed.The Cu Cl coupled with DPPF(1,1-bis(diphenylphosphino)ferrocene)was assig...A strategy for copper-catalyzed and biphosphine ligand controlled boracarboxylation of 1,3-dienes and CO_(2) with 3,4-selectivity was developed.The Cu Cl coupled with DPPF(1,1-bis(diphenylphosphino)ferrocene)was assigned to be the best catalyst,with 84%yield and exclusive3,4-selectivity.The ligand effect on both catalytic activity and regioselectivity of boracarboxylation was disclosed,which is rarely reported in any copper catalyzed boracarboxylation.The borocupration process is revealed to be a vital step for the biphosphine participated boracarboxylation of 1,3-dienes with CO_(2).The minimal substrate distortion occurring in 3,4-borocupration favors the 3,4-regioselectivity of boracarboxylation.The“pocket”confinement and suitableβ_(n)(92°–106°)of bisphosphine ligands are demonstrated to be in favour of the interaction between LCu-Bpin complex(the catalytic precursor)and1,3-diene substrate to decrease their interaction energyΔE_(int)(ζ)in 3,4-borocupration,thus promoting the 3,4-boracarboxylation.展开更多
文摘碳环构筑在药物与功能材料合成中至关重要,炔烃广泛应用于环合反应,但碳环合成仍具挑战。因此,新型炔烃碳环化策略成为研究热点,其中RATC策略为碳环构筑提供了新思路。本文介绍了RATC反应的研究进展,分子内RATC反应如Heiba等多取代环戊烷制备、刘心元等6(5)-6-5稠环构建及Studer等1-三氟甲基炔丙基环戊烷合成。随后,文章探讨分子间RATC策略,介绍了李金恒等以1,4-二氧六环为自由基前体的Inter-RATC反应和张国柱等通过Inter-RATC构建环丁烷的反应,尽管存在局限性,但它们为碳环构筑提供了新方法。The construction of carbon rings is crucial in the synthesis of pharmaceuticals and functional materials. Alkynes are widely used in cyclization reactions, yet the synthesis of carbon rings remains challenging. Therefore, novel alkyne carbon cyclization strategies have become a research hotspot, among which the RATC strategy offers new insights into carbon ring construction. This article introduces the research progress of RATC reactions, focusing on intramolecular RATC reactions such as the preparation of multisubstituted cyclopentanes by Heiba et al., the construction of 6(5)-6-5 fused rings by Liu et al. and the synthesis of 1-trifluoromethylallylcyclopentanes by Studer et al. Subsequently, the article explores intermolecular RATC strategies, presenting the Inter-RATC reaction using 1,4-dioxane as a radical precursor by Li et al. and the construction of cyclobutanes through Inter-RATC by Zhang et al. Despite their limitations, these strategies provide novel methods for carbon ring construction.
基金the National Key R&D Program of China(No.2022YFB4101900)National Natural Science Foundation of China(Nos.22278305,U21B2096)Natural Science Foundation of Tianjin City(No.23JCZDJC00040)。
文摘A strategy for copper-catalyzed and biphosphine ligand controlled boracarboxylation of 1,3-dienes and CO_(2) with 3,4-selectivity was developed.The Cu Cl coupled with DPPF(1,1-bis(diphenylphosphino)ferrocene)was assigned to be the best catalyst,with 84%yield and exclusive3,4-selectivity.The ligand effect on both catalytic activity and regioselectivity of boracarboxylation was disclosed,which is rarely reported in any copper catalyzed boracarboxylation.The borocupration process is revealed to be a vital step for the biphosphine participated boracarboxylation of 1,3-dienes with CO_(2).The minimal substrate distortion occurring in 3,4-borocupration favors the 3,4-regioselectivity of boracarboxylation.The“pocket”confinement and suitableβ_(n)(92°–106°)of bisphosphine ligands are demonstrated to be in favour of the interaction between LCu-Bpin complex(the catalytic precursor)and1,3-diene substrate to decrease their interaction energyΔE_(int)(ζ)in 3,4-borocupration,thus promoting the 3,4-boracarboxylation.
