Imine Reduction with Me2S-BH3

Although there exists a variety of different catalysts for hydroboration of organic substrates such as aldehydes, ketones, imines, nitriles etc., recent evidence suggests that tetra-coordinate borohydride species, formed by activation, redistribution, or decomposition of boron reagents, are the true hydride donors. We then proposed that Me2S-BH3 could also act as a hydride donor for the reduction of various imines, as similar compounds have been observed to reduce carbonyl substrates. This boron reagent was shown to be an effective and chemoselective hydroboration reagent for a wide variety of imines.

Visible-Light Radical–Radical Coupling vs. Radical Addition: Disentangling a Mechanistic Knot

A highly enantioselective protocol has been recently described as allowing the synthesis of five-membered cyclic imines harnessing the selective generation of a β-Csp3-centered radical of acyl heterocyclic derivatives and its subsequent interaction with diverse NH-ketimines. The overall transformation represents a novel cascade process strategy crafted by individual well-known steps; however, the construction of the new C-C bond highlights a crucial knot from a mechanistically perspective. We believe that the full understanding of this enigmatic step may enrich the current literature and expand latent future ideas. Therefore, a detailed mechanistic study of the protocol has been conducted. Here, we provide theoretical insight into the mechanism using quantum chemistry calculations. Two possible pathways have been investigated: (a) imine reduction followed by radical–radical coupling and (b) radical addition followed by product reduction. In addition, investigations to unveil the origin behind the enantioselectivity of the 1-pyrroline derivatives have been conducted as well.

Synthesis of Chiral Amines by C–C Bond Formation with Photoredox Catalysis

Chiral amines are key substructures of biologically active natural products and drug candidates. The advent of photoredox catalysis has changed the way synthetic chemists think about building these substructures, opening new pathways that were previously unavailable. New developments in this area are reviewed, with an emphasis on C–C bond constructions involving radical intermediates generated through photoredox processes.1 Introduction2 Radical–Radical Coupling of α-Amino Radicals2.1 Radical–Radical Coupling Involving Amine Oxidation2.2 Radical–Radical Coupling Involving Imine Reduction2.3 Couplings Involving both Amine Oxidation and Imine Reduction3 Addition Reactions of α-Amino Radicals3.1 Conjugate Additions of α-Amino Radicals3.2 Addition of α-Amino Radicals to Heteroaromatic Systems3.3 Cross Coupling via Additions to Transition Metal Complexes4 Radical Addition to C=N Bonds Using Photoredox Catalysis4.1 Intramolecular Radical Addition to C=N Bonds4.2 Intermolecular Radical Addition to C=N Bonds5 Conclusion

Mechanistic insight into B(C6F5)3 catalyzed imine reduction with PhSiH3 under stoichiometric water conditions

Hydrosilylation or amination products? It depends on water amount and nucleophiles like excess water or produced/added amines.

Characterization of imine reductases in reductive amination for the exploration of structure-activity relationships

Imine reductases (IREDs) have shown great potential as catalysts for the asymmetric synthesis of industrially relevant chiral amines, but a limited understanding of sequence activity relationships makes rational engineering challenging. Here, we describe the characterization of 80 putative and 15 previously described IREDs across 10 different transformations and confirm that reductive amination catalysis is not limited to any particular subgroup or sequence motif. Furthermore, we have identified another dehydrogenase subgroup with chemoselectivity for imine reduction. Enantioselectivities were determined for the reduction of the model substrate 2-phenylpiperideine, and the effect of changing the reaction conditions was also studied for the reductive aminations of 1-indanone, acetophenone, and 4-methoxyphenylacetone. We have performed sequence-structure analysis to help explain clusters in activity across a phylogenetic tree and to inform rational engineering, which, in one case, has conferred a change in chemoselectivity that had not been previously observed.

Bifunctional thiosquaramide catalyzed asymmetric reduction of dihydro-β-carbolines and enantioselective synthesis of (−)-coerulescine and (−)-horsfiline by oxidative rearrangement

A simple and efficient asymmetric synthesis of THBCs through a chiral thiosquaramide 11b catalyzed imine reduction of dihydro-β-carbolines (17a−f) and syntheses of (−)-coerulescine and (–)-horsfiline via enantioselective oxidative rearrangement.

A diversity of recently reported methodology for asymmetric imine reduction

This review describes recent developments in enantioselective imine reduction, including related substrates in which a CN bond is the target for reduction, and in situ methods.