Highly Z-Selective Julia–Kocienski Olefination Using N-Sulfonylimines and Its Mechanistic Insights from DFT Calculations
Takuma Chizaki, Koichi Fujiwara, Junko Fujimoto, Tetsuo Narumi, Satoshi Shuto, and Mizuki Watanabe
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.