Synthesis of 8,10- and 9,10-disubstituted camphor derivatives

Dadson, William M.; Lam, Mayda; Money, T.; Piper, Susan E.

doi:10.1139/v83-061

Cited by 21 publications

(8 citation statements)

References 5 publications

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“…Camphor can easily be converted into many mono‐ and dibromo‐substituted derivatives, which are useful intermediates in ligand synthesis 14. Especially attractive for the synthesis of functionalized diphosphanes are 9,10‐ and 8,10‐dibromocamphors 6a and 6b , available from camphor by stereospecific bromination/rearrangement reaction sequences 15. Thus, the bromomethyl groups in 6a and 6b can be advantageously used for nucleophilic substitution with phosphorus nucleophiles to obtain 7a and 7b , whereas the carbonyl group can be further converted into, for example, the hydroxy group by reduction, giving rise to hydroxy derivative of the diphosphanes 8a and 8b , or transformed into an acetal group ( 9a , 9b ) 16…”

Section: Resultsmentioning

confidence: 99%

“…(1 S ,4 R ,7 R )‐1,7‐Bis(iodomethyl)‐7‐methylbicyclo[2.2.1]heptan‐2‐one (10a): A solution of 9,10‐dibromocamphor (10 g, 32.2 mmol), obtained as described previously,15 and KI (53.5 g, 322.0 mmol) in dry DMF (150 mL) was stirred under argon at 110 °C overnight. A precipitate formed.…”

Section: Methodsmentioning

confidence: 99%

“…(1 S ,4 R ,7 S )‐1,7‐Bis(iodomethyl)‐7‐methylbicyclo[2.2.1]heptan‐2‐one (10b): This compound was obtained analogously to 10a , from 8,10‐dibromocamphor, obtained as described previously,15 in 81.5% yield. White crystals, m.p.…”

Section: Methodsmentioning

confidence: 99%

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Chiral Oxo- and Oxy-Functionalized Diphosphane Ligands Derived from Camphor for Rhodium(I)-Catalyzed Enantioselective Hydrogenation

Komarov¹,

Monsees²,

Spannenberg³

et al. 2003

Eur. J. Org. Chem.

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The synthesis of two series of diastereomeric oxo-and oxysubstituted diphosphanes 7a−9a and 7b−9b, as well as an analogous nonfunctionalized diphosphane 17, was performed starting from (R)-camphor. The new diphosphanes were used as ligands in the enantioselective rhodium(I)-catalyzed hydrogenation of functionalized olefins − α-and β-dehydroamino acids and their esters − in order to elucidate the [a] effect of the oxo-and oxy-functional groups. The enantioselectivities, ranging from 2−90% ee, and the rates were strongly dependent on the type and relative position of the oxo or oxy substituent in the catalyst. Possible explanations for the effects are given.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Chiral Oxo- and Oxy-Functionalized Diphosphane Ligands Derived from Camphor for Rhodium(I)-Catalyzed Enantioselective Hydrogenation

Komarov¹,

Monsees²,

Spannenberg³

et al. 2003

Eur. J. Org. Chem.

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“…These substituents can then be further modified. [44][45][46][47] T h e r e are a number of reactions which lead to the exposure of chiral cyclopentane intermediates.…”

Section: Cn Co 2 Etmentioning

confidence: 99%

Chiral Cyclic Synthetic Intermediates from Readily Available Monoterpenoids

Hanson

2015

Journal of Chemical Research

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“…Herein we would like to present our investigation for the recyclization reactions of easily available 8,10-dibromocamphor [31] with…”

Section: Introductionmentioning

confidence: 99%

Recyclization reactions of 8,10-dibromocamphor with Grignard and organolithium compounds

Verenka

Gorichko

2021

Fr. Ukr. J. Chem.

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Grignard reagents and organolithium compounds react with 8,10-dibromocamphor to afford substituted 1-methyl-2-methylenebicyclo[3.2.0]heptanes. Recyclization proceeds via intramolecular enolate alkylation and Grob fragmentation of the reaction intermediates. All compounds have been characterized by 1H, 13C and 19F NMR spectroscopy and their chemical composition proved by HRMS analyses. The relative spatial arrangement of substituents in the molecule of (1-methyl-2-methylenebicyclo[3.2.0]heptan-6-yl)diphenylmethanol was studied by NOESY experiments.

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Synthesis of 8,10- and 9,10-disubstituted camphor derivatives

Abstract: Regiospecific bromination and debromination reactions have been used to provide a synthetic route from camphor to optically active 8,10- and 9,10-disubstituted camphor derivatives.

Cited by 21 publications

References 5 publications

Chiral Oxo- and Oxy-Functionalized Diphosphane Ligands Derived from Camphor for Rhodium(I)-Catalyzed Enantioselective Hydrogenation

Chiral Oxo- and Oxy-Functionalized Diphosphane Ligands Derived from Camphor for Rhodium(I)-Catalyzed Enantioselective Hydrogenation

Chiral Cyclic Synthetic Intermediates from Readily Available Monoterpenoids

Recyclization reactions of 8,10-dibromocamphor with Grignard and organolithium compounds

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