Iodocyclization of Allylic Alcohol Derivatives Containing Internal Nucleophiles. Control of Stereoselectivity by Substituents in the Acyclic Precursors

A. Richard Chamberlin, Milana Dezube, Patrick Dussault, Mark C. McMills

Research output: Contribution to journalArticle

145 Citations (Scopus)

Abstract

The effect of various substituents on the diastereoselectivity of a number of kinetically controlled iodocyclizations has been studied. The reaction of 3-hydroxy-4-alkenoic acids (1a-n) with iodine in a neutral two-phase medium gives stereoselective ring closure, usually to the m-3-hydroxy-4-iodoalkyl lactone. The stereoselectivity is unaffected by protection of alcohol moiety (lb,c), but replacement of the hydroxyl group with a methyl substituent (1e) lowers the stereoselectivity significantly. A 2-methyl substituent (1j-m) can have a dramatic effect on the diastereoselectivity of the reaction. Esters and ketones (l0a-c) undergo a related iodocyclization with similar stereoselectivity. In the absence of an internal nucleophile (13,16) iodohydrin formation results in reversed diastereoselectivity of iodine attack.

Original languageEnglish (US)
Pages (from-to)5819-5825
Number of pages7
JournalJournal of the American Chemical Society
Volume105
Issue number18
DOIs
StatePublished - Sep 1983

Fingerprint

Stereoselectivity
Nucleophiles
Iodine
Alcohols
Derivatives
Lactones
Ketones
Hydroxyl Radical
Esters
Carboxylic acids
Acids
allyl alcohol

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Iodocyclization of Allylic Alcohol Derivatives Containing Internal Nucleophiles. Control of Stereoselectivity by Substituents in the Acyclic Precursors. / Chamberlin, A. Richard; Dezube, Milana; Dussault, Patrick; McMills, Mark C.

In: Journal of the American Chemical Society, Vol. 105, No. 18, 09.1983, p. 5819-5825.

Research output: Contribution to journalArticle

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N2 - The effect of various substituents on the diastereoselectivity of a number of kinetically controlled iodocyclizations has been studied. The reaction of 3-hydroxy-4-alkenoic acids (1a-n) with iodine in a neutral two-phase medium gives stereoselective ring closure, usually to the m-3-hydroxy-4-iodoalkyl lactone. The stereoselectivity is unaffected by protection of alcohol moiety (lb,c), but replacement of the hydroxyl group with a methyl substituent (1e) lowers the stereoselectivity significantly. A 2-methyl substituent (1j-m) can have a dramatic effect on the diastereoselectivity of the reaction. Esters and ketones (l0a-c) undergo a related iodocyclization with similar stereoselectivity. In the absence of an internal nucleophile (13,16) iodohydrin formation results in reversed diastereoselectivity of iodine attack.

AB - The effect of various substituents on the diastereoselectivity of a number of kinetically controlled iodocyclizations has been studied. The reaction of 3-hydroxy-4-alkenoic acids (1a-n) with iodine in a neutral two-phase medium gives stereoselective ring closure, usually to the m-3-hydroxy-4-iodoalkyl lactone. The stereoselectivity is unaffected by protection of alcohol moiety (lb,c), but replacement of the hydroxyl group with a methyl substituent (1e) lowers the stereoselectivity significantly. A 2-methyl substituent (1j-m) can have a dramatic effect on the diastereoselectivity of the reaction. Esters and ketones (l0a-c) undergo a related iodocyclization with similar stereoselectivity. In the absence of an internal nucleophile (13,16) iodohydrin formation results in reversed diastereoselectivity of iodine attack.

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