Chemoenzymatic Hunsdiecker-Type Decarboxylative Bromination of Cinnamic Acids

Huanhuan Li; Sabry H H Younes; Shaohang Chen; Peigao Duan; Chengsen Cui; Ron Wever; Wuyuan Zhang; Frank Hollmann

doi:10.1021/acscatal.2c00485

Chemoenzymatic Hunsdiecker-Type Decarboxylative Bromination of Cinnamic Acids

ACS Catal. 2022 Apr 15;12(8):4554-4559. doi: 10.1021/acscatal.2c00485. Epub 2022 Apr 4.

Authors

Huanhuan Li^{1

2}, Sabry H H Younes^{3

4}, Shaohang Chen², Peigao Duan¹, Chengsen Cui^{2

5}, Ron Wever⁶, Wuyuan Zhang^{2

5}, Frank Hollmann³

Affiliations

¹ School of Chemical Engineering and Technology, Xi'an Jiaotong University, Xi'an 710049, China.
² Tianjin Institute of Industrial Biotechnology, Chinese Academy of Sciences, 32 West 7th Avenue, Tianjin 300308, China.
³ Department of Biotechnology, Delft University of Technology, Van der Maasweg 9, Delft 2629HZ, The Netherlands.
⁴ Department of Chemistry, Faculty of Sciences, Sohag University, Sohag 82524, Egypt.
⁵ National Center of Technology Innovation for Synthetic Biology, 32 West 7th Avenue, Tianjin 300308, China.
⁶ Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Amsterdam 1098 XH, The Netherlands.

Abstract

In this contribution, we report chemoenzymatic bromodecarboxylation (Hunsdiecker-type) of α,ß-unsaturated carboxylic acids. The extraordinarily robust chloroperoxidase from Curvularia inaequalis (CiVCPO) generated hypobromite from H₂O₂ and bromide, which then spontaneously reacted with a broad range of unsaturated carboxylic acids and yielded the corresponding vinyl bromide products. Selectivity issues arising from the (here undesired) addition of water to the intermediate bromonium ion could be solved by reaction medium engineering. The vinyl bromides so obtained could be used as starting materials for a range of cross-coupling and pericyclic reactions.