Stereospecific Suzuki, Sonogashira, and Negishi Coupling Reactions of N‑Alkoxyimidoyl Iodides and Bromides

• Published in: Journal of organic chemistry 2013-04, Vol.78 (8), p.3676-3687
• Main Authors: Dolliver, Debra D, Bhattarai, Bijay T, Pandey, Arjun, Lanier, Megan L, Bordelon, Amber S, Adhikari, Sarju, Dinser, Jordan A, Flowers, Patrick F, Wills, Veronica S, Schneider, Caroline L, Shaughnessy, Kevin H, Moore, Jane N, Raders, Steven M, Snowden, Timothy S, McKim, Artie S, Fronczek, Frank R
• Format: Article
• Language: English
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo400179u

A high-yielding stereospecific route to the synthesis of single geometric isomers of diaryl oxime ethers through Suzuki coupling of N-alkoxyimidoyl iodides is described. This reaction occurs with complete retention of the imidoyl halide geometry to give single E- or Z-isomers of diaryl oxime ethers. The Sonogashira coupling of N-alkoxyimidoyl iodides and bromides with a wide variety of terminal alkynes to afford single geometric isomers of aryl alkynyl oxime ethers has also been developed. Several of these reactions proceed through copper-free conditions. The Negishi coupling of N-alkoxyimidoyl halides is introduced. The E and Z configurations of nine Suzuki-coupling products and two Sonogashira-coupling products were confirmed by X-ray crystallography.