Effective Enzymatic Synthesis of Benzotropolone and Formation Mechanism of Its Bicyclooctane‐type Intermediate

In this study, 1′,2′‐dihydroxy‐3,4‐benzotropolone (BTP), the simplest theaflavins (TFs) derivative, is synthesized via the oxidative coupling of pyrogallol (PG) and catechol (CC). We show that low temperature was beneficial to the production of BTP. A possible generation mechanism of the key bicyclo...

Full description

Saved in:
Bibliographic Details
Published in:Asian journal of organic chemistry 2023-09, Vol.12 (9)
Main Authors: Ding, Yangping, Gao, Zhijiang, Jinjin Jian, Chen, Bingcan
Format: Article
Language:English
Subjects:
Catechol
Controllability
Low temperature
Organic chemistry
Quantum chemistry
Quinones
Substrates
Synthesis
Tautomers
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:In this study, 1′,2′‐dihydroxy‐3,4‐benzotropolone (BTP), the simplest theaflavins (TFs) derivative, is synthesized via the oxidative coupling of pyrogallol (PG) and catechol (CC). We show that low temperature was beneficial to the production of BTP. A possible generation mechanism of the key bicyclo[3.2.1]octane‐type intermediate (BOI) during the formation process of BTP was subsequently proposed. Our analysis based on quantum chemical calculations indicated that three types of tautomers of PG quinones should be present in the reaction solution. Among them, PG quinone tautomer III (PGQT‐III) with two carbanions might be one of the direct substrates for BOI synthesis, which underwent 1,6‐addition reaction to C3‐C4 bond of ortho‐quinone with strong electrophilicity leading to the key intermediate. Furthermore, the presence of PGQT‐III was also supported by the retrosynthetic analysis of BOI. The findings not only shed light on the production mechanism of BTP, but also create new prospects in synthesizing TFs with controllable products.
ISSN:2193-5807
2193-5815
DOI:10.1002/ajoc.202300327