Diastereoselective ortho-lithiation of [5]ferrocenophanes

Škvorcová, Andrea; Rakovský, Erik; Kožı́šek, Jozef; Šebesta, Radovan

doi:10.1016/j.jorganchem.2011.04.006

Cited by 7 publications

(2 citation statements)

References 28 publications

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“…DFT calculations, only recently started to help explain the underlying reasons for diastereoselection in ortho-lithiations of ferrocene derivatives. 27,28 We have studied diastereoselective ortho-lithiations of ferrocenophanes 29 and have suggested the mechanism of dilithiation reaction leading to the Taniaphos family of ligands. 30 A lack of understanding of the lithiation of ferrocenes prompted us to investigate diastereoselective ortho-lithiations of three relevant ferrocene compounds by DFT calculations.…”

Section: Introductionmentioning

confidence: 99%

Computational study of diastereoselective ortho-lithiations of chiral ferrocenes

Škvorcová

Šebesta

2014

Org. Biomol. Chem.

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Diastereoselective ortho-lithiations serve for the preparation of many important chiral ferrocenes, however diastereoselections of these lithiations are explained only by simple steric models. We elucidated ortho-lithiations of three important ferrocenes based on DFT calculations. The calculations showed that simple models of transition states involving ferrocenyl substrates and lithium bases can only in some cases account for the experimental results. Transition state models, which include solvent or coordinating additives as distinct entities bound to lithium, can satisfactorily explain diastereoselection of the ortho-lithiations of chiral ferrocenes.

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Section: Introductionmentioning

confidence: 99%

Computational study of diastereoselective ortho-lithiations of chiral ferrocenes

Škvorcová

Šebesta

2014

Org. Biomol. Chem.

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“…In the last few decades it has been found that Ugi’s approach is applicable to related substrates, revealing almost the same stereoselectivities regarding ortho-directed lithiation and nucleophilic substitution of the amine moiety. This includes utilization of N , N -dimethyl-1-ferrocenylalkylamines and -benzylamines ( 85 ), ,− homoannularly bridged N , N -α-dimethylamino-1,2-tetramethylene ferrocenes ( 86 ), − heteroannularly bridged [3] ( 87 , ,− 88 , )- and [5]ferrocenophanes ( 89 ) , as well as bisferrocenyldiamines ( 90 ) (Chart ). The enantiopure starting materials 85 – 90 have been made available among others by resolution, ,, asymmetric reductions of ferrocenyl ketones ,,,,,,, and imines, , asymmetric alkylation/arylation of ferrocenealdehydes, , and the use of enantiomerically pure cyclopentadienes or cyclopentadienyl ligands. ,,, …”

Section: Ortho-directed Metalationmentioning

confidence: 99%

Selective Syntheses of Planar-Chiral Ferrocenes

2013

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Planar-chiral ferrocenes are widely applied in catalytic asymmetric transformations in scientific research as well as in industry. A plethora of different methodologies have been developed to access these molecules with a high degree of regio- and stereoselectivity. The aim of this contribution is to give a comprehensive overview of this topic. The synthesis of 1,2- and 1,3-substituted ferrocenes by electrophilic aromatic substitution, ortho-directed metalation, kinetic resolution, and desymmetrization is discussed. Advantages and disadvantages are highlighted.

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Retro‐Brook Rearrangement of Ferrocene‐Derived Silyl Ethers

Bariak

Malastová

Almássy

et al. 2015

Chemistry A European J

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An intramolecular Li-Si exchange was observed on various lithiated ferrocenylbenzyl silyl ethers. The thermodynamically more stable C-silylated isomers were isolated in good yields and fully characterized. The reaction mechanism of the [1,4] retro-Brook rearrangement was investigated by DFT calculations. Two distinct reaction routes were proposed and a possible stabilization effect of the ferrocenyl fragment on the C-silylated isomers was described. The diastereoselective rearrangement of the trimethylsilyl group to the ortho position of the ferrocenyl cyclopentadienyl ring was also accomplished and the absolute configuration of the product was determined.

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Diastereoselective ortho-lithiation of [5]ferrocenophanes

Cited by 7 publications

References 28 publications

Computational study of diastereoselective ortho-lithiations of chiral ferrocenes

Computational study of diastereoselective ortho-lithiations of chiral ferrocenes

Selective Syntheses of Planar-Chiral Ferrocenes

Retro‐Brook Rearrangement of Ferrocene‐Derived Silyl Ethers

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