Issue 17, 2022

Synthesis of aryl-fused 1,4-oxathiepines from pyridinium 1,4-zwitterionic thiolates and vinylidene ortho-quinone methides

Abstract

The synthesis of aryl-fused 1,4-oxathiepines from pyridinium 1,4-zwitterionic thiolates with ortho-alkynyl aromatic phenols has been achieved in good to excellent yields under mild conditions. The key reactive intermediates (i.e., vinylidene ortho-quinone methides) are readily generated in situ from α-alkynylnaphthalen-2-ols and they can also be generated from 2-alkynylphenols successfully by rationally varying the substituent of the phenyl ring according to computational results. Replacing vinylidene ortho-quinone methides (VQMs) with common ortho-quinone methides (QMs) was also investigated, and benzooxathiepine can be obtained in a moderate yield with (2-(bromomethyl)phenoxy)(tert-butyl)dimethylsilane as the QM precursor. Moreover, a preliminary study of the catalytic asymmetric version of this novel (3 + 4) reaction was attempted, affording a unique axially chiral arene-acyclic alkene scaffold with moderate enantioselectivity.

Graphical abstract: Synthesis of aryl-fused 1,4-oxathiepines from pyridinium 1,4-zwitterionic thiolates and vinylidene ortho-quinone methides

Supplementary files

Article information

Article type
Research Article
Submitted
07 May 2022
Accepted
08 Jul 2022
First published
11 Jul 2022

Org. Chem. Front., 2022,9, 4612-4618

Synthesis of aryl-fused 1,4-oxathiepines from pyridinium 1,4-zwitterionic thiolates and vinylidene ortho-quinone methides

Y. He, P. Wu, X. Zhang, T. Wang, Q. Tao, K. Zhou, Z. Ouyang, H. Zhai, D. Cheng and B. Cheng, Org. Chem. Front., 2022, 9, 4612 DOI: 10.1039/D2QO00735E

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