ChemInform Abstract: Catalytic Asymmetric Allylic Alkylation with a Novel P‐S Bidentate Ligand.

Kang, Jahyo; Yu, Shaoze; Kim, J. I.; Cho, H. G.

doi:10.1002/chin.199546112

Cited by 2 publications

(3 citation statements)

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“…Therefore, we started the calculations with diastereomeric binaphthyl-based phosphite-thioether ligands L1 and L2 , which contain an easy to compute methyl thioether group and fixed configurations of the biphenyl phosphite moiety (Figure ). It is to note that this type of heterodonor binaphthyl-based P, thioether led to the first applications of P,S ligands in asymmetric processes, such as hydroformylation, hydrogenation, and allylic alkylations . However, the fact that only promising results were reached in allylic alkylation limited further developments, in contrast to the high applicability and success of BINAP-type ligands.…”

Section: Introductionmentioning

confidence: 99%

Density Functional Theory-Inspired Design of Ir/P,S-Catalysts for Asymmetric Hydrogenation of Olefins

et al. 2021

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In silico-based optimization of Ir/P,S-catalysts for the asymmetric hydrogenation of unfunctionalized olefins using (E)-1-(but-2-en-2-yl)-4-methoxybenzene as a benchmark olefin has been carried out. DFT calculations revealed that the thioether group has a major role in directing the olefin coordination. This, together with the configuration of the biphenyl phosphite group, has an impact in maximizing the energy gap between the most stable transition states leading to opposite enantiomers. As a result, the optimized catalyst proved to be efficient in the hydrogenation of a range of alkenes with the same substitution pattern and olefin geometry as the benchmark olefin, regardless of the presence of functional groups with different coordination abilities (ee values up to 97%). Appealingly, further modifications at the thioether groups and at the biaryl phosphite moiety allowed the highly enantioselective hydrogenation of olefins with different substitution patterns (e.g., α,β-unsaturated lactones and lactams, 1,1′-disubstituted enol phosphinates, and cyclic β-enamides; ee values up to >99%).

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Section: Introductionmentioning

confidence: 99%

Density Functional Theory-Inspired Design of Ir/P,S-Catalysts for Asymmetric Hydrogenation of Olefins

et al. 2021

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“…However, axially chiral biaryls bearing thioether moieties are rare in the literature compared with phosphine or amine analogues 22 but hold appealing structures for their application in asymmetric catalysis 23 and feature interesting bioactivities. 24 With this motivation, we wondered whether a thioether as the Lewis base and a carbonyl group as a weak Lewis acid would be a competent Lewis pair able to promote the labilization of a stereogenic axis on the basis of the discussed strategy.…”

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confidence: 99%

“…However, we speculated whether the repulsive/attractive force balance could be reverted in a sterically more relaxed heterobiaryl scaffold featuring a five-membered ring. 7a Considering that the introduction of a thioether moiety in functionalized axially chiral 3-aryl indoles could open new avenues for not only chiral ligands 23 but also drug candidates, 24 we decided to explore the suitability of the LABI-based DKR strategy to the resolution of trisubstituted 3-aryl indole scaffolds 1 bearing an aldehyde and a thioether groups at ortho , ortho′ positions ( Scheme 1 D).…”

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confidence: 99%

Dynamic Kinetic Resolution of Indole-Based Sulfenylated Heterobiaryls by Rhodium-Catalyzed Atroposelective Reductive Aldol Reaction

Rodríguez-Franco,

Ros,

Merino

et al. 2023

ACS Catal.

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A highly enantio-and diastereoselective dynamic kinetic resolution (DKR) of configurationally labile 3-aryl indole-2carbaldehydes is described. The DKR proceeds via a Rh-catalyzed intermolecular asymmetric reductive aldol reaction with acrylate esters, with simultaneous generation of three stereogenic elements. The strategy relies on the labilization of the stereogenic axis that takes place thanks to a transient Lewis acid−base interaction (LABI) between the formyl group and a thioether moiety strategically located at the ortho′ position. The atropisomeric indole products present a high degree of functionalization and can be further converted to a series of axially chiral derivatives, thereby expanding their potential application in drug discovery and asymmetric catalysis.

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ChemInform Abstract: Catalytic Asymmetric Allylic Alkylation with a Novel P‐S Bidentate Ligand.

Cited by 2 publications

References 0 publications

Density Functional Theory-Inspired Design of Ir/P,S-Catalysts for Asymmetric Hydrogenation of Olefins

Density Functional Theory-Inspired Design of Ir/P,S-Catalysts for Asymmetric Hydrogenation of Olefins

Dynamic Kinetic Resolution of Indole-Based Sulfenylated Heterobiaryls by Rhodium-Catalyzed Atroposelective Reductive Aldol Reaction

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