A Planar‐Chiral Palladium Complex Derived from a Weak Oxygen Donor <i>N,N</i>‐Diisopropyl Ferrocenecarboxamide Ligand

Thorat, Raviraj Ananda; Mandhar, Yogesh; Parganiha, Devendra; Patil, Khushbu Bindesh; Singh, Vikram; Shakir, Batul; Raju, Saravanan; Kumar, Sangit

doi:10.1002/slct.202203945

Cited by 4 publications

(1 citation statement)

References 56 publications

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“…[53][54][55] Our group has studied the C-H activation in ferrocene for the construction of carbon-carbon and carbon-heteroatom (heteroatom = S/Se/Te) bonds. [56][57][58][59][60][61][62] Further, a variety of directing groups have been studied along with various coupling partners, namely alkanes, arenes, aryl halides, alkenes, and alkynes with ferrocenes by others and us. 44,[54][55][56][57][58][59][60] However, allene substrates have not been used, which are known to undergo [4+1] and [4+2] annulation reactions affording five and six-membered rings, respectively.…”

Section: Introductionmentioning

confidence: 99%

Rh(III)-Catalyzed [4+3] Annulation: Temperature Dependent Ste-reodivergent Synthesis of Point-Planar Chiral Ferrocene Fused Azepines

Thorat,

Parganiha,

Jain

et al. 2023

Preprint

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Planar chiral ferrocenes are extensively investigated structures in asymmetric catalysis, materials science, and medicinal chemistry. Although, the synthetic approaches for six-membered fused planar chiral ferrocenes are well-established, the construction of a seven-membered fused ring via [4+3] annulation has remained unexplored and seems to be challenging. Allenes are valuable synthons and well explored for [4+1] and [4+2] annulation but not yet explored for [4+3] annulation. Herein, an efficient rhodium-catalyzed temperature-dependent stereodivergent [4+3] annulation reaction has been devel-oped for the synthesis of novel seven-membered ferrocenylazepines via C-H activation of substituted ferrocene-p-tosylamides with allenes. At room temperature, Rh-catalyzed [4+3] annulation selectively offered one diastereomer (>20:1 dr), whereas at 60 ºC, another diastereomer was obtained exclusively with >20:1 dr. Further, [4+3] annulation reaction in the presence of a chiral RhCpX catalyst (2.0 mol %) yielded chiral ferrocenyl azepines in 56% yield and up to 90:10 er. Mecha-nistic investigations by control experiments and isotopic labeling study suggested that the reaction proceeds via a formation of a σ-bonded rhodacycle, having low energy due to less steric repulsion between the phenyl ring of allene and Cp*(pentamethyl cyclopentadienyl), which upon reductive elimination offered kinetically controlled diastereomer at room temperature. Under heating (60 ºC) conditions, kinetically controlled diastereomer undergo CH-allylic isomerization to af-ford completely thermodynamically controlled diastereomer, which has also been observed experimentally and computa-tionally for isolated kinetically controlled diastereomer.

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Section: Introductionmentioning

confidence: 99%

Rh(III)-Catalyzed [4+3] Annulation: Temperature Dependent Ste-reodivergent Synthesis of Point-Planar Chiral Ferrocene Fused Azepines

Thorat,

Parganiha,

Jain

et al. 2023

Preprint

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Synthesis of 2-oxazoline ferrocenes: Towards high-efficient chiral ligands and catalysts

Dai

Yang

2023

Journal of Organometallic Chemistry

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Temperature-Dependent Diastereodivergent [4 + 3] Annulation: Synthesis of Ferrocene-Fused Azepines via Rh(III) Catalysis

Thorat,

Parganiha,

Jain

et al. 2024

Org. Lett.

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Herein, we disclose the first temperature-dependent diastereodivergent [4 + 3] annulation of ferrocene-p-tosylamides via C−H activation with allenes by a Rh catalyst. At room temperature, Rh-catalyzed [4 + 3] annulation selectively offered a kinetically controlled diastereomer [>20:1 diastereomeric ratio (dr)], whereas at 60 °C, a thermodynamically controlled diastereomer was obtained exclusively with >20:1 dr.

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A Planar‐Chiral Palladium Complex Derived from a Weak Oxygen Donor N,N‐Diisopropyl Ferrocenecarboxamide Ligand

Cited by 4 publications

References 56 publications

Rh(III)-Catalyzed [4+3] Annulation: Temperature Dependent Ste-reodivergent Synthesis of Point-Planar Chiral Ferrocene Fused Azepines

Rh(III)-Catalyzed [4+3] Annulation: Temperature Dependent Ste-reodivergent Synthesis of Point-Planar Chiral Ferrocene Fused Azepines

Synthesis of 2-oxazoline ferrocenes: Towards high-efficient chiral ligands and catalysts

Temperature-Dependent Diastereodivergent [4 + 3] Annulation: Synthesis of Ferrocene-Fused Azepines via Rh(III) Catalysis

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