Sensitive functional groups are tolerated in an iodine–zinc exchange reaction catalyzed by Li(acac). Aryl and heteroaryl diorganozinc compounds with keto, aldehyde, or isothiocyanate substituents can be prepared by this method (see example in scheme; acac=acetylacetone, NMP=1‐methyl‐2‐pyrrolidinone). Such zinc reagents serve as substrates for a wide variety of coupling reactions.
A series of symmetrical and unsymmetrical N,N'-disubstituted aminotroponimines (ATIHs) have been prepared. Substituents ranging from linear to cyclic alkyl groups, chelating ethers, and aryl groups were employed. The corresponding aminotroponiminate zinc complexes were then synthesized and characterized by a number of techniques, including by X-ray crystallography. Herein we report on the investigations into their activity in the intramolecular hydroamination of nonactivated alkenes. We also demonstrate that complexes bearing ligands with cyclic alkyl groups show superior activity in a number of selected reactions with functionalized aminoalkenes.
The new zinc compound N-cyclohexyl-2-(cyclohexylamino)troponiminate zinc methyl, [(Cy)2ATI]ZnMe, was synthesized and showed a superior reactivity in the intramolecular hydroamination reaction of non-activated alkenes compared to previously reported homogeneous zinc complexes.
The electronically modified zinc complex 5-phenylsulfanyl-N-isopropyl-2-(isopropylamino)troponiminate zinc methyl, [(PhS-ATI(iPr)2)ZnMe], was synthesized. It showed an increased reactivity in the intramolecular hydroamination reaction of non-activated alkenes compared to a previously-reported, non-substituted complex.
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