Electroreductive Carboxylation of Propargylic Acetates with CO2: Access to Tetrasubstituted 2,3-Allenoates

Jing-Hao Qin; Zhi-Qiang Xiong; Chaozhihui Cheng; Ming Hu; Jin-Heng Li

doi:10.1021/acs.orglett.3c03735

Electroreductive Carboxylation of Propargylic Acetates with CO₂: Access to Tetrasubstituted 2,3-Allenoates

Org Lett. 2023 Dec 29;25(51):9176-9180. doi: 10.1021/acs.orglett.3c03735. Epub 2023 Dec 19.

Authors

Jing-Hao Qin¹, Zhi-Qiang Xiong¹, Chaozhihui Cheng^{1

2}, Ming Hu^{1

3}, Jin-Heng Li^{1

3

4

5}

Affiliations

¹ Key Laboratory of Jiangxi Province for Persistent Pollutants Control and Resources Recycle, Nanchang Hangkong University, Nanchang 330063, China.
² Key Laboratory of Organic Chemistry of Jiangxi Province, Jiangxi Science & Technology Normal University, Nanchang 330013, China.
³ State Key Laboratory Base of Eco-Chemical Engineering, College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, China.
⁴ State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, China.
⁵ School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 475004, China.

PMID: 38113454
DOI: 10.1021/acs.orglett.3c03735

Abstract

An electroreductive carboxylation of propargylic alcohols with CO₂ and then workup with TMSCHN₂ to construct tetrasubstituted 2,3-allenoates is developed. This method allows the incorporation of an external ester group into the resulting allene system through electroreduction, carboxylation, and deacetoxylation cascades. Mechanistically, electricity on/off experiments and cyclic voltammetry analysis support the preferential generation of the CO₂ radical anion or the 3-aryl propargylic acetate radical anion based on the electron nature of the aryl rings.