Recent Developments in Asymmetric Allylic Amination Reactions

Abstract

The asymmetric synthesis of allylic amines is an important research area in modern synthetic organic chemistry, primarily due to the inherent utility and ubiquity of this functional group in various synthetic intermediates and bioactive agents. For instance, a plethora of methods for the stereocontrolled construction of allylic amines now provides a vibrant array of strategies for the installation of this important functionality. This review highlights developments in the field since 1998 through the provision of the most important methods and their mechanistic aspects in order to provide insight into their current scope and limitations. Hence, we envisage it will be an essential guide to the current state-of-the-art for this important area, which highlights potential new opportunities for further developments.

Biomacromolecule-Assisted Screening for Reaction Discovery and Catalyst Optimization

“…As it turned out, the promising results seen with Ni(0) as catalyst and the rate acceleration seen with bidentate phosphine ligands by ISES set the stage for the discovery of the first catalytic, asymmetric allylic amination with Ni reported by Maiti and Berkowitz in 2004 . To this day, this remains the key precedent for exploiting earth-abundant Ni for asymmetric allylic amination reaction …”

“…172 To this day, this remains the key precedent for exploiting earth-abundant Ni for asymmetric allylic amination reaction. 204 These observations derived from key ISES-screening results in 2004 appear to have stimulated work elsewhere on Ni(0)mediated allylic substitution chemistry. In 2015, the Mashima group described the amination of allylic alcohols using a Ni(0) catalyst to give products 19 and 23 (Scheme 3).…”

Recent Advances in the Enantioselective Synthesis of Chiral Amines via Transition Metal-Catalyzed Asymmetric Hydrogenation

“…A relevant number of new metal-catalyzed transformations for the synthesis of chiral amines have been reported. Important achievements have been made in enantioselective methods involving, among others, reductive amination, − hydroamination, − allylic amination, or isomerization reactions. , The metal-catalyzed enantioselective alkyl addition to imines has also been explored . Nonetheless, the asymmetric reduction of unsaturated compounds continues to be the most fundamental means of introducing chirality .…”

Improved Synthesis of MediPhos Ligands and Their Use in the Pd‐Catalyzed Enantioselective N‐Allylation of Glycine Esters

“…In the course of our research into conformationally restricted proline‐derived dipeptide mimetics (ProMs) [5] we recently became interested in the catalytic asymmetric synthesis of amino acid‐derived allylic amines under configurational control. However, while many successful examples have been reported for the use of simple amines as nucleophiles in enantioselective Pd‐catalyzed allylic substitutions, [2e–f,6] we recognized that amino acid derivatives represent difficult substrates in such reactions, and, accordingly, only few examples have been reported [7]…”