Synthesis, stereochemical assignment, and enantioselective catalytic activity of late transition metal planar chiral complexes

Laws, David; Poff, Christopher D.; Heyboer, Ethan M; Blakey, Simon B.

doi:10.1039/d3cs00325f

Cited by 7 publications

(2 citation statements)

References 65 publications

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“…Unfortunately, it works reliably only using TLC and is not suitable for column chromatography. Further investigations are required to find a more efficient chiral auxiliary ligand which would enable large-scale separation (see discussion of possible separation procedures in several papers 21,22 and reviews 23,24 ).…”

Section: Resultsmentioning

confidence: 99%

Rhodium complexes with planar-chiral cyclopentadienyl ligands: synthesis from tert-butylacetylene and catalytic performance in C–H activation of arylhydroxamates

Kolos,

Nelyubina,

Podyacheva

et al. 2023

Dalton Trans.

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Section: Resultsmentioning

confidence: 99%

Rhodium complexes with planar-chiral cyclopentadienyl ligands: synthesis from tert-butylacetylene and catalytic performance in C–H activation of arylhydroxamates

Kolos,

Nelyubina,

Podyacheva

et al. 2023

Dalton Trans.

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“…Additionally, they noted that the indenyl ligand was critical for reactivity, with the analogous [Cp*RhCl 2 ] 2 catalyst resulting in significantly reduced yields. Inspired by this precedent, we sought to render the aziridination enantioselective through the use of our planar chiral Rh(III) indenyl catalyst 2 , developed in the context of an enantioselective allylic C–H amidation reaction (Scheme b, bottom). , Herein, we report the development of an enantioselective aziridination method targeting unactivated alkenes using a simple hydroxylamine in combination with a planar chiral Rh(III) indenyl catalyst (Scheme c). Furthermore, we detail our computational investigations into the mechanism of this reaction.…”

Section: Introductionmentioning

confidence: 99%

Enantioselective Aziridination of Unactivated Terminal Alkenes Using a Planar Chiral Rh(III) Indenyl Catalyst

Gross,

Im,

Laws

et al. 2024

J. Am. Chem. Soc.

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Chiral aziridines are important structural motifs found in natural products and various target molecules. They serve as versatile building blocks for the synthesis of chiral amines. While advances in catalyst design have enabled robust methods for enantioselective aziridination of activated olefins, simple and abundant alkyl-substituted olefins pose a significant challenge. In this work, we introduce a novel approach utilizing a planar chiral rhodium indenyl catalyst to facilitate the enantioselective aziridination of unactivated alkenes. This transformation exhibits a remarkable degree of functional group tolerance and displays excellent chemoselectivity favoring unactivated alkenes over their activated counterparts, delivering a wide range of enantioenriched high-value chiral aziridines. Computational studies unveil a stepwise aziridination mechanism in which alkene migratory insertion plays a central role. This process results in the formation of a strained four-membered metallacycle and serves as both the enantio-and rate-determining steps in the overall reaction.

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[2.2]Benzoindenophane‐Based Chiral Indenyl Ligands: Design, Synthesis, and Applications in Asymmetric C−H Activation

Guo,

Jiang,

Wang

2024

Angewandte Chemie

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Development of chiral indenyl ligands for asymmetric C–H activation is a longstanding challenge, and extremely few successes have been achieved. In this paper, we describe a class of readily accessible, facilely tunable and user‐friendly chiral indenyl ligands featuring a [2.2]benzoindenophane skeleton via a divergent synthesis strategy. The corresponding chiral indenyl rhodium catalysts were successfully applied in the asymmetric C–H activation reaction of O‐Boc hydroxybenzamide with alkenes to give various chiral dihydroisoquinolone products (up to 97% yield, up to 98% ee). Moreover, the asymmetric C–H activation reaction of carboxylic acids with alkynes was also successfully accomplished, providing a range of axially chiral isocoumarins (up to 99% yield, up to 94% ee). Notably, this represents the first example of enantioselective transition metal catalyzed C(sp2)‐H activation/oxidative coupling of benzoic acids with internal alkynes to construct isocoumarins. Given many attractive features of this class of indenyl ligands, such as convenient synthesis, high tunability and exclusive face‐selectivity of coordination, its applications in more catalytic asymmetric C–H activation and in other asymmetric catalysis are foreseen.

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Synthesis, stereochemical assignment, and enantioselective catalytic activity of late transition metal planar chiral complexes

Abstract: Planer chiral complexes emerge as powerful tools for enantioselective catalysis.

Cited by 7 publications

References 65 publications

Rhodium complexes with planar-chiral cyclopentadienyl ligands: synthesis from tert-butylacetylene and catalytic performance in C–H activation of arylhydroxamates

Rhodium complexes with planar-chiral cyclopentadienyl ligands: synthesis from tert-butylacetylene and catalytic performance in C–H activation of arylhydroxamates

Enantioselective Aziridination of Unactivated Terminal Alkenes Using a Planar Chiral Rh(III) Indenyl Catalyst

[2.2]Benzoindenophane‐Based Chiral Indenyl Ligands: Design, Synthesis, and Applications in Asymmetric C−H Activation

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