Citation: Yuefei Gu, Tianyang Wang, Ming Gao, Zhu-Jun Yao. Scalable Cu(Ⅱ)-mediated intramolecular dehydrogenative phenol-phenol coupling: Concise synthesis of enantiopure axially chiral homo- and hetero-diphenols[J]. Chinese Chemical Letters, ;2021, 32(1): 380-384. doi: 10.1016/j.cclet.2020.02.015 shu

Scalable Cu(Ⅱ)-mediated intramolecular dehydrogenative phenol-phenol coupling: Concise synthesis of enantiopure axially chiral homo- and hetero-diphenols

State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China

gaom@nju.edu.cn

yaoz@nju.edu.cn

Received Date: 15 January 2020
Revised Date: 21 January 2020
Accepted Date: 10 February 2020
Available Online: 11 February 2020

Figures(4)

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.
- Axially chirality,
- Dehydrogenative phenol-phenol coupling,
- Cu(Ⅱ)-mediated oxidation,
- Chiral auxiliary,
- Diastereoselectivity
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