Laboratorium für Organische Chemie, HCI H335, Eidgenössische Technische Hochschule Zürich, Vladimir-Prelog-Weg 3, 8093, Zürich, Switzerland.
Angew Chem Int Ed Engl. 2019 Jul 8;58(28):9537-9541. doi: 10.1002/anie.201903090. Epub 2019 May 30.
Morpholine ketene aminal is employed in iridium-catalyzed asymmetric allylic alkylation reactions as a surrogate for amide enolates to prepare γ,δ-unsaturated β-substituted morpholine amides. Kinetic resolution or, alternatively, stereospecific substitution affords the corresponding products in high enantiomeric excess. The utility of the products generated by this method has been showcased by their further elaboration into amines, ketones, or acyl silanes. A putative catalytic intermediate (η -allyl)iridium(III) with achiral P,Olefin-ligand was synthetized and characterized for the first time.
吗啉酮烯胺在铱催化的不对称烯丙基烷基化反应中被用作酰胺烯醇化物的替代物，用于制备γ,δ-不饱和β-取代吗啉酰胺。动力学拆分或立体特异性取代以高对映过量获得相应的产物。通过该方法生成的产物的用途已通过将其进一步衍生为胺、酮或酰基硅烷得到展示。首次合成并表征了具有手性 P,Olefin-配体的假定催化中间体（η-烯丙基）三价铱。
