Effect of Tethered, Axially Coordinated Ligands (TACLs) on Dirhodium(II,II) Catalyzed Cyclopropanation: A Linear Free Energy Relationship Study

Zavala, Cristian; Darko, Ampofo

doi:10.1021/acs.joc.2c00020

Cited by 5 publications

(3 citation statements)

References 73 publications

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“…We were curious if more drastic changes to the ligand might furnish valuable insights to drive future catalyst design. Two dinuclear Rh catalysts developed by the Darko group, (Rh 2 (OAc) 3 ( p -OMe-ArTCB) and Rh 2 (OAc) 3 ( p -NO 2 -ArTCB), where one of the -OAc ligands of Rh 2 (OAc) 4 is replaced with a bridging N/S ligand (Scheme A) gave no change in the product distribution (entries 6,7) …”

Section: Resultsmentioning

confidence: 99%

“…Two dinuclear Rh catalysts developed by the Darko group, (Rh 2 (OAc) 3 (p-OMe-ArTCB) and Rh 2 (OAc) 3 (p-NO 2 -ArTCB), where one of the -OAc ligands of Rh 2 (OAc) 4 is replaced with a bridging N/S ligand (Scheme 6A) gave no change in the product distribution (entries 6,7). 41 We were pleased to find that a Rh 2 (espn) 2 Cl complex (entry 5), 42 where the typical bridging carboxylate ligand is replaced with a bridging carboxamidate ligand, reversed the product distribution in favor of azetidine 3cc over dehydropiperidine 4cc in a 3:1 ratio. Catalyst control was also observed using 1b (Scheme 6B), where Rh 2 (esp) 2 gave a 3.2:1 ratio of 4bc over 3bc; the selectivity was reversed using Rh 2 (espn) 2 Cl to 7.2:1 in favor of 3bc.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Tunable Divergent Reactivity of Aziridinium Ylides in the Synthesis of Complex Piperidines and Azetidines

Dehghany,

Pavaneli,

Kailing

et al. 2024

ACS Catal.

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Nitrogenated heterocycles comprise the cores of a number of synthetically useful compounds, including pharmaceuticals, bioactive natural products, agrochemicals, and other drug-like molecules. The widespread interest in methods to increase the fraction of sp 3 carbon atoms (Fsp 3 ) of drug-like scaffolds in a stereocontrolled manner, while enabling explorations of unusual amine chemical space, inspired our efforts to tune the reactivity of aziridinium ylides. A sequential nitrene−carbene transfer of simple allenes leads to divergent product outcomes depending on the nature of the carbene precursor, furnishing products of different ring sizes. In addition, the catalyst control over the ring size via proposed hydrogen-bonding interactions between the catalyst and substrate was explored. Computational studies were employed to gain insight into the major features of substrates and catalysts that influence the tunable reactivity of aziridinium ylide intermediates formed in this chemistry.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Tunable Divergent Reactivity of Aziridinium Ylides in the Synthesis of Complex Piperidines and Azetidines

Dehghany,

Pavaneli,

Kailing

et al. 2024

ACS Catal.

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show abstract

“…These catalysts replace one of the -OAc ligands of Rh2(OAc)4 with a bridging N/S ligand, as shown in Scheme 6A; however, the presence of the N/S bridging ligand with sulfur position as an axial ligand gave no change in the product distribution (entries 6-7). 41 We were pleased to find that a Rh2(espn)2Cl complex (entry 5), 42 where the typical bridging carboxylate ligand has been replaced with a bridging amide ligand, reversed the product distribution in favor of the azetidine 3cc over the dehydropiperidine 4cc by a ratio of 3:1. This catalyst control was also observed using 1b (Scheme 6B), where Rh2(esp)2 gave a 3.2:1 ratio of piperidine 4bc over azetidine 3bc; the selectivity was reversed using Rh2(espn)2Cl to 7. of 3bc.…”

Section: Approaches To Control Product Outcomes the Brief Catalyst Sc...mentioning

confidence: 99%

Tunable Divergent Reactivity of Aziridinium Ylides in the Synthesis of Complex Piperidines and Azetidines

Dehghany,

Pavaneli,

Kailing

et al. 2023

Preprint

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Nitrogenated heterocycles comprise the cores of a number of synthetically useful compounds, including pharmaceuticals, bioactive natural products, agrochemicals and other drug-like molecules. The widespread interest in methods to increase the fraction of sp3 carbon atoms (Fsp3) of drug-like scaffolds in a stereocontrolled manner, while enabling explorations of novel amine chemical space, inspired our efforts to harness the divergent reactivity of aziridinium ylides for the rapid preparation of new azetidine and piperidine scaffolds. A sequential nitrene-carbene transfer of simple allenes can furnish divergent product outcomes depending on the nature of the carbene precursor or the catalyst identity. Computational studies were employed to shed insight into the major factors that influence the tunable reactivity of the aziridinium ylide intermediates formed in this chemistry.

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Self‐Supported Heterogeneous Dirhodium(II) Catalyst for Nitrene and Carbene Transfer Reactions

Satheesh,

Alahakoon,

Shrestha

et al. 2024

Eur J Org Chem

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The bimetallic rhodium(II) paddlewheel (Rh2A4) complex is one of the most reactive classes of rhodium catalysts, well‐renowned for the most demanding carbene‐ and nitrene‐transfer reactions. In view of its importance in modern synthetic chemistry, we herein report a facile approach for preparing a self‐supported and reusable dirhodium(II) polymer‐based heterogeneous catalyst through a reductive ligation protocol. The catalyst displays good reactivity for inter‐ and intramolecular nitrene‐ and carbene‐insertions of various olefins, and can also engage in C–H insertion of hydrocarbon derivatives, all under ambient conditions. The catalyst reusability is expected to empower the use of these precious metal catalysts at industrial scales.

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Effect of Tethered, Axially Coordinated Ligands (TACLs) on Dirhodium(II,II) Catalyzed Cyclopropanation: A Linear Free Energy Relationship Study

Cited by 5 publications

References 73 publications

Tunable Divergent Reactivity of Aziridinium Ylides in the Synthesis of Complex Piperidines and Azetidines

Tunable Divergent Reactivity of Aziridinium Ylides in the Synthesis of Complex Piperidines and Azetidines

Tunable Divergent Reactivity of Aziridinium Ylides in the Synthesis of Complex Piperidines and Azetidines

Self‐Supported Heterogeneous Dirhodium(II) Catalyst for Nitrene and Carbene Transfer Reactions

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