Catalytic Asymmetric Allylic Amination with Isatins, Sulfonamides, Imides, Amines, and N-Heterocycles

Abstract

A generally useful palladium-catalyzed method for the asymmetric allylic amination with a large variety of isatins, sulfonamides, imides, amines, and N-heterocycles is introduced. A single protocol with a readily available catalyst accomplishes this reaction at room temperature with high yields and enantioselectivities often exceeding 90%, which is demonstrated with 31 examples.

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

“…In 2020 Wolf’s group reported the use of the Pd/( S )- t -Bu-PHOX catalyst for the allylic amination of several 1,3-diaryl allyl acetates with a range of isatins, sulfonamides, imides, amines and several N -heterocycles ( Scheme 61 ). 203 …”

“…In 2020 Wolf's group reported the use of the Pd/(S)-t-Bu-PHOX catalyst for the allylic amination of several 1,3-diaryl allyl acetates with a range of isatins, sulfonamides, imides, amines and several N-heterocycles (Scheme 61). 203 Among the new applications of known variants of PHOX ligands we highlight the work by Malcolmson's group on the allylic alkylation of acyclic 1,3-dienes with C-nucleophiles, such as Meldrum's acid derivatives, β-diketones, and malononitriles using the electron-deficient PHOX derivative L55 and triethylamine as base (Scheme 62). 204,205 An excess of triethylamine was needed to form the monoalkylated product selectively.…”

Iridium-catalysed reductive allylic amination of α,β-unsaturated aldehydes

“…In this context, important efforts to employ various allyl electrophilic reagents, including allylic halides, 4 esters, 5 and alcohols, 6 were made to afford N -allylic amines. Further, in this regard, various protocols based on Pd, 7 Ir, 8 Ru, 9 Rh, 10 Au, 11 Co, 12 Pt, 13 Fe, 14 Ni, 15 and organic catalysts 16 were developed to realize this transformation. Successful allylic C–H amination using Pd, 17 Ru, 18 Rh, 19 Fe, 20 and other species 21 as catalysts for the construction of N -allylic amine products were also reported.…”

New P,Nsp3ligands for palladium-catalyzed asymmetric allylic substitutions

“…Notable unsymmetrical ligands applied in AAS include PHOX (Fig. 1), 8 IndoPHOX, 9 RuPHOX, 10 Phosferrox, 11 Josiphos, 12 FerroNPS, 13 etc . Despite remarkable advances in chiral ligand design, some of the ligands are still rarely tolerated by a wide range of substrates, and each type of substrate often requires a particular ligand to obtain excellent enantioselectivity.…”