Scalable Cu(II)-mediated intramolecular dehydrogenative phenol-phenol coupling: Concise synthesis of enantiopure axially chiral homo- and hetero-diphenols
Scalable Cu(II)-mediated intramolecular dehydrogenative phenol-phenol coupling: Concise synthesis of enantiopure axially chiral homo- and hetero-diphenols
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可扩展的 Cu(II) 介导的分子内脱氢苯酚-苯酚偶联：对映体纯轴向手性同二酚和杂二酚的简明合成
DOI：
10.1016/j.cclet.2020.02.015
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发表时间：
2021
影响因子：
9.1
通讯作者：
Yao Zhu-Jun
中科院分区：
文献类型：
--
作者：
Gu Yuefei;Wang Tianyang;Gao Ming;Yao Zhu-Jun
以((4S，5S)-2，2-dimethyl-1，3-dioxolane-4，5-diyl)dimethanol为手性助剂，在温和的铜(II)催化条件下，成功地建立了苯酚分子内脱氢同异偶联反应，用于快速合成对映体轴联苯酚。商业上可获得的(R)-α-甲基苄胺被确定为反应中铜(II)的最佳胺配体。考察了各种同/异双羟基苯甲酸酯底物，得到了相应的轴向手性二酚类化合物，并尝试了一种具有代表性的可伸缩制剂。本工作以一种轴向手性二苯酚为合成中间体，实现了天然产物(+)-五味子甲素的正式合成。
An intramolecular dehydrogenative homo- and hetero-coupling of phenols has been successfully developed for quick preparation of enantiopure axial diphenols under mild Cu(II)-mediated conditions, using ((4S,5S)-2,2-dimethyl-1,3-dioxolane-4,5-diyl)dimethanol as the chiral auxiliary. The commercially available (R)-α-methylbenzylamine was identified as the best amine ligand for Cu(II) in the reactions. A variety of homo/hetero bis-dihydroxylbenzoate substrates were examined, affording the corresponding axially chiral diphenols with satisfactory to excellent diastereomeric ratios, and a representative scalable preparation was also attempted. A formal synthesis of natural product (+)-deoxyschizandrin has been achieved in this work using one axially chiral diphenol as the synthetic intermediate.