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Highly Z-Selective Julia-Kocienski Olefination Using N-Sulfonylimines and Its Mechanistic Insights from DFT
Takuma Chizaki1, Koichi Fujiwara1, Junko Fujimoto2
1Faculty of Pharmaceutical Sciences, Hokkaido University, Kita-12, Nishi-6, Kita-ku, Sapporo 060-0812, Japan.
Abstract:
The Julia-Kocienski (JK) olefination is effective for E-selective olefination, but highly Z-selective versions remain rare. Here, we report a highly Z-selective JK olefination (Z ratio >99:1) using N-sulfonylimines as electrophiles instead of aldehydes. This method demonstrates a broad substrate scope, tolerating electron-donating and -withdrawing groups, amides, halogens, carboxylic acids, and hydroxyls. Z-selectivity in our system arises from both the 1,2-addition and Smiles rearrangement steps without involving synperiplanar elimination. This study expands the toolkit for Z-selective olefin synthesis.
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