HOTf-Catalyzed Alkyl-Heck-type Reaction

Huan Zhou; Liang Ge; Jinshuai Song; Wujun Jian; Yajun Li; Chunsen Li; Hongli Bao

doi:10.1016/j.isci.2018.04.020

HOTf-Catalyzed Alkyl-Heck-type Reaction

iScience. 2018 May 25:3:255-263. doi: 10.1016/j.isci.2018.04.020. Epub 2018 May 1.

Authors

Huan Zhou¹, Liang Ge¹, Jinshuai Song², Wujun Jian², Yajun Li², Chunsen Li³, Hongli Bao⁴

Affiliations

¹ State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 155 Yangqiao Road West, Fuzhou, Fujian 350002, People's Republic of China; University of Chinese Academy of Sciences, Beijing 100049, People's Republic of China.
² State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 155 Yangqiao Road West, Fuzhou, Fujian 350002, People's Republic of China.
³ State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 155 Yangqiao Road West, Fuzhou, Fujian 350002, People's Republic of China. Electronic address: chunsen.li@fjirsm.ac.cn.
⁴ State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 155 Yangqiao Road West, Fuzhou, Fujian 350002, People's Republic of China; Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 155 Yangqiao Road West, Fuzhou, Fujian 350002, People's Republic of China. Electronic address: hlbao@fjirsm.ac.cn.

Abstract

The Heck reaction, along with other cross-coupling reactions, led to a revolution in organic chemistry. In the last 50 years, metal-catalyzed, photo-induced, or base-mediated Heck and Heck-type reactions have been elegantly developed. Brønsted acid-catalyzed Heck (or Heck-type) reactions are still unknown, however. By introducing alkyl peroxides as the key intermediates, primary, secondary, and tertiary aliphatic carboxylic acids are therefore applied here in a one-pot Brønsted acid-catalyzed Heck-type reaction, to deliver E-alkenes exclusively in most cases. The use of HOTf is vital to the reaction, whose mechanism is supported by both experimental and computational results. This method can be expanded to the direct alkylation of complex natural products.

Keywords: Natural Product Synthesis; Organic Chemistry Methods; Organic Synthesis.