Stereospecific Suzuki, Sonogashira, and Negishi Coupling Reactions ofN-Alkoxyimidoyl Iodides and Bromides

Abstract

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.

Synthesis of C4-alkynylisoxazoles via a Pd-catalyzed Sonogashira cross-coupling reaction

“…The 1 H NMR spectral data are in good agreement with the literature data. 20 (Z)-1-Phenyloct-2-yn-1-one O-methyl oxime (2d). Prepared according to general procedure (II).…”

Recent Advances in Bromination of Aromatic and Heteroaromatic Compounds

“…35 The performed study was based on the previously proposed stereospecific method for synthesizing the E-and Z-isomers of benzophenone oxime ethers. 36…”

C−H Activation and Cross‐Coupling of Acyclic Aldonitrone

“…Arylation of double C=N bonds can be achieved in Pd‐catalyzed processes with halogenated substrates, such as chloroimines [14] or N ‐alkoxyimidoyl halides, [15] or even in a metal free reaction of oxime chlorides with arylboronic acids [16] . Transition metal‐catalyzed arylation of H−C=N−X systems involving functionalization of the C(sp 2 )−H bond generally requires additional directing groups (pyridine, pyrimidine, etc.)…”