Electrocyclic Ring-Opening Reactions of <i>gem</i>-Dibromocyclopropanes in the Synthesis of Natural Products and Related Compounds

Halton, Brian; Harvey, Joanne E.

doi:10.1055/s-2006-948193

Cited by 12 publications

(1 citation statement)

References 76 publications

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“…[1][2][3][4][5][6][7][8][9][10][11] These compounds are excellent building blocks due to their availability in high enantiomeric purity, simple techniques of preparation, and a substantial synthetic potential of the cyclopropane ring. [12][13][14][15] For example, they were utilized in the asymmetric synthesis of pyrethroids 1,2 and other natural products, 3,4 stereoregular oligocyclopropanes, 5 chiral biaryls, 6 and liquid crystals. 7 In a recent article we efficiently resolved racemic trans-2,2-dichloro-3-methylcyclopropanecarboxylic acid into enantiomers 1.…”

Section: Introductionmentioning

confidence: 99%

Chiral methyl trans-2,2-dichloro-3-methylcyclopropanecarboxylate upon exposure to thiophenolate nucleophile

Kovalenko¹

2013

Arkivoc

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Substitution of the β-halogen atoms in methyl (1R,3S)-2,2-dichloro-3-methylycyclopropanecarboxylate with sodium thiophenolate leads to the di(phenylthio) ester (1RS,3S)-4 as a mixture of diastereomers. The cis-trans isomerisation of methyl (1RS,3S)-3-methyl-2,2-bis(phenylthio)-cyclopropanecarboxylate 4, basic hydrolysis and subsequent crystallization gave the corresponding acid (1R,3S)-5 in high diastereomeric and enantiomeric purity. On the other hand, ring opening of the ester (1RS,3S)-4 under acidic conditions leads to methyl 3-methyl-4,4-di(phenylthio)prop-3-enoate (8) or the chiral S-phenyl thioester methyl (3S)-3-methyl-4-oxo-4-(phenylthio)butanoate (7).

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