Regio- and stereoselective synthesis of vicinal fluorohydrins

Haufe, Günter

doi:10.1016/j.jfluchem.2004.01.023

Cited by 61 publications

(33 citation statements)

References 148 publications

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“…Ring opening of diepoxide 14 was firstly explored with pyridine.HF [13,14]. This resulted in an efficient conversion but to the rather unexpected difluorodiol 18.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of selectively fluorinated cyclohexanes: The observation of phenonium rearrangements during deoxyfluorination reactions on cyclohexane rings with a vicinal phenyl substituent

Bykova

Al‐Maharik

Slawin

et al. 2015

Journal of Fluorine Chemistry

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A study focused on the synthesis of a derivative of all-cis phenyl-2,3,5,6-tetrafluorocyclohexane, incorporating a methyl group at the benzylic position, found that the fluorination reactions of diepoxide and diol precursors, were susceptible to rearrangement and unexpected products. The origin of these rearranged products can be rationalised by aryl migrations occurring via phenonium ion intermediates, in adventitious pathways occurring during deoxofluorination reactions with hydrogen fluoride reagents.We dedicate this paper to Professor Veronique Gouverneur in recognition of her 2015 ACS Award for Creative work in Fluorine Chemistry.

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“…Ring opening of diepoxide 14 was firstly explored with pyridine.HF [13,14]. This resulted in an efficient conversion but to the rather unexpected difluorodiol 18.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of selectively fluorinated cyclohexanes: The observation of phenonium rearrangements during deoxyfluorination reactions on cyclohexane rings with a vicinal phenyl substituent

Bykova

Al‐Maharik

Slawin

et al. 2015

Journal of Fluorine Chemistry

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“…Combined with its robustness, this new synthetic route to fluorinated carbocycles complements other approaches that typically involve nucleophilic fluorination rather than electrophilic fluorination. [17] The products are versatile fluorinated building blocks offering multiple possibilities for further functional-group manipulations of the double bond. A detailed study of the synthetic scope of these new building blocks and related compounds is ongoing in our laboratory.…”

Section: Resultsmentioning

confidence: 99%

Sequential Desymmetrization–Fluorination: Enantioselective Synthesis of Fluorinated Cyclitols

Purser

Odell

Claridge

et al. 2006

Chemistry A European J

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An asymmetric synthesis of enantioenriched, highly functionalized fluorinated carbocycles has been developed based on an enantioselective Sharpless dihydroxylation of cyclohexadienylsilanes, combined with a diastereoselective electrophilic fluorodesilylation. Several parameters define the level of diastereocontrol for the fluorination step. These include the relative stereochemistry of the starting endocyclic allylsilanes and the structural features of the reactants. As expected for an S(E)2' mechanism, the fluorodesilylation occurred with clean transposition of the double bond, with the attack of the electrophilic fluorinating agent taking place preferentially anti to the silyl group. For the fluorination step, the best selectivities were observed for the monocyclic anti,syn benzyl-protected precursors and for the syn,syn starting allylsilane. Full NMR spectroscopic analysis of the fluorinated monocyclic compounds, which possess an endocyclic double bond flanked by two electronegative groups (the methoxy group and the fluorine substituent) revealed that a subtle combination of steric (1,3-axial/pseudoaxial interaction) and stereoelectronic effects (pi-sigma* interaction) favours the preferential conformers featuring the methoxy group in a pseudoaxial position.

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“…For the preparation of optically active fluorohydrins [21], we intended kinetic resolution by lipase-catalyzed hydrolysis of the corresponding acetates 2, which were prepared by treatment of the 2-fluoroalken-3-ols 1 with acetic anhydride or chloroacetic anhydride in the presence of pyridine. As a model compound for the resolution experiments we chose 3-acetoxy-2-fluorodec-1-ene (2a).…”

Section: Synthesis and Resolution Of Racemic 2-fluoroalk-1-en-3-ols Amentioning

confidence: 99%

Synthesis of optically active 2-fluoroalk-1-en-3-yl esters and chirality transfer in their Claisen-type rearrangements

Marhold

Wittmann

Takahashi

et al. 2007

Journal of Fluorine Chemistry

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Regio- and stereoselective synthesis of vicinal fluorohydrins

Cited by 61 publications

References 148 publications

Synthesis of selectively fluorinated cyclohexanes: The observation of phenonium rearrangements during deoxyfluorination reactions on cyclohexane rings with a vicinal phenyl substituent

Synthesis of selectively fluorinated cyclohexanes: The observation of phenonium rearrangements during deoxyfluorination reactions on cyclohexane rings with a vicinal phenyl substituent

Sequential Desymmetrization–Fluorination: Enantioselective Synthesis of Fluorinated Cyclitols

Synthesis of optically active 2-fluoroalk-1-en-3-yl esters and chirality transfer in their Claisen-type rearrangements

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