Synthesis of Altenuene Backbones through Iodine(III)-Participated Umpolung Diesterification and Insights into the General [1,5]-H Shift in para-Dearomatization of Phenols via Quantum Chemical Calculations

Dan Luo; Liangzhen Hu; Tianyong Gao; Xiaohui Zhang; Yan Xiong

doi:10.1021/acs.joc.1c02915

Synthesis of Altenuene Backbones through Iodine(III)-Participated Umpolung Diesterification and Insights into the General [1,5]-H Shift in para-Dearomatization of Phenols via Quantum Chemical Calculations

J Org Chem. 2022 Apr 15;87(8):5065-5075. doi: 10.1021/acs.joc.1c02915. Epub 2022 Apr 4.

Authors

Dan Luo¹, Liangzhen Hu¹, Tianyong Gao¹, Xiaohui Zhang¹, Yan Xiong^{1

2

3}

Affiliations

¹ School of Chemistry and Chemical Engineering, and Chongqing Key Laboratory of Theoretical and Computational Chemistry, Chongqing University, Chongqing 401331, China.
² State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China.
³ School of Chemical and Environmental Engineering, and Collaborative Innovation Center for High Value Transformation of Coal Chemical Process By-products, Xinjiang Institute of Engineering, Xinjiang 830091, China.

PMID: 35377643
DOI: 10.1021/acs.joc.1c02915

Abstract

Through PhI(OAc)₂-oxidized dearomatization and diesterification of 3'-hydroxy-[1,1'-biphenyl]-2-carboxylic acids, a series of polycyclic compounds possessing an altenuene backbone were obtained in moderate to good yields. The Umpolung diesterification reaction was completed under mild reaction conditions without an additional nucleophilic reagent. This work offers a concise method for the synthesis of diverse natural altenuene analogues. The mechanism was proposed, and the [1,5]-H shift was studied in isomerization from the ketone-form structure to a phenol employing computational studies.