Mechanistic study on the side arm effect in a palladium/Xu-Phos-catalyzed enantioselective alkoxyalkenylation of γ-hydroxyalkenes

Shuai Zhu, Zihao Ye, Ming-Jie Chen, Lei Wang, Yu-Zhuo Wang, Ke-Nan Zhang, Wen-Bo Li, Han-Ming Ding, Zhiming Li () and Junliang Zhang ()
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Shuai Zhu: East China Normal University
Zihao Ye: Fudan University
Ming-Jie Chen: East China Normal University
Lei Wang: Yangzhou University
Yu-Zhuo Wang: East China Normal University
Ke-Nan Zhang: East China Normal University
Wen-Bo Li: East China Normal University
Han-Ming Ding: East China Normal University
Zhiming Li: Fudan University
Junliang Zhang: East China Normal University

Nature Communications, 2023, vol. 14, issue 1, 1-11

Abstract: Abstract Recently, the asymmetric bifunctionalization of alkenes has received much attention. However, the development of enantioselective alkoxyalkenylation has posed a considerable challenge and has lagged largely behind. Herein, we report a new palladium-catalyzed enantioselective alkoxyalkenylation reaction, using a range of primary, secondary, and tertiary γ-hydroxy-alkenes with alkenyl halides. By employing newly identified Xu-Phos (Xu8 and Xu9) with a suitable side-arm adjacent to the PCy2 motif, a series of allyl-substituted tetrahydrofurans were obtained in good yields with up to 95% ee. Besides (E)-alkenyl halides, (Z)-alkenyl halide was also examined and provided the corresponding (Z)-product as a single diastereomer, supporting a stereospecific oxidative addition and reductive elimination step. Moreover, deuterium labeling and VCD experiments were employed to determine a cis-oxypalladation mechanism. DFT calculations helped us gain deeper insight into the side-arm effect on the chiral ligand. Finally, the practicability of this method is further demonstrated through a gram-scale synthesis and versatile transformations of the products.

Date: 2023
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DOI: 10.1038/s41467-023-43202-5

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