Mild stereoselective formation of tri- and tetrasubstituted olefins by regioselective ring opening of 1,1-disubstituted vinyl oxiranes with dialkyl dithiophosphates

Boying Guo, Edon Vitaku, Jon T Njardarson

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

Presented in this Letter is a mild new method to stereoselectively ring open 1,1-disubstituted vinyl oxiranes using dialkyl dithiophosphate nucleophiles. This new reaction proceeds in toluene at room temperature to afford tri- and tetrasubstituted allylic alcohols with high Z-selectivity. The syn relationship between the alcohol and the newly incorporated dithiophosphate moiety presented an opportunity to evaluate the anionic hopping properties of the ring opening product. Treatment of the ring opening product with base results in a facile phosphate hopping followed by a selective thiolate 3-exo-trig instead of a 5-exo-tet cyclization.

Original languageEnglish (US)
Pages (from-to)3232-3234
Number of pages3
JournalTetrahedron Letters
Volume55
Issue number21
DOIs
StatePublished - May 21 2014

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Nucleophiles
Cyclization
Toluene
Alkenes
Phosphates
Alcohols
Temperature
allyl alcohol
3,4-epoxy-1-butene

Keywords

  • Dithiophosphoric acid
  • Regioselective
  • Ring opening
  • Vinyl oxirane
  • Z-Selective

ASJC Scopus subject areas

  • Biochemistry
  • Organic Chemistry
  • Drug Discovery

Cite this

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title = "Mild stereoselective formation of tri- and tetrasubstituted olefins by regioselective ring opening of 1,1-disubstituted vinyl oxiranes with dialkyl dithiophosphates",
abstract = "Presented in this Letter is a mild new method to stereoselectively ring open 1,1-disubstituted vinyl oxiranes using dialkyl dithiophosphate nucleophiles. This new reaction proceeds in toluene at room temperature to afford tri- and tetrasubstituted allylic alcohols with high Z-selectivity. The syn relationship between the alcohol and the newly incorporated dithiophosphate moiety presented an opportunity to evaluate the anionic hopping properties of the ring opening product. Treatment of the ring opening product with base results in a facile phosphate hopping followed by a selective thiolate 3-exo-trig instead of a 5-exo-tet cyclization.",
keywords = "Dithiophosphoric acid, Regioselective, Ring opening, Vinyl oxirane, Z-Selective",
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T1 - Mild stereoselective formation of tri- and tetrasubstituted olefins by regioselective ring opening of 1,1-disubstituted vinyl oxiranes with dialkyl dithiophosphates

AU - Guo, Boying

AU - Vitaku, Edon

AU - Njardarson, Jon T

PY - 2014/5/21

Y1 - 2014/5/21

N2 - Presented in this Letter is a mild new method to stereoselectively ring open 1,1-disubstituted vinyl oxiranes using dialkyl dithiophosphate nucleophiles. This new reaction proceeds in toluene at room temperature to afford tri- and tetrasubstituted allylic alcohols with high Z-selectivity. The syn relationship between the alcohol and the newly incorporated dithiophosphate moiety presented an opportunity to evaluate the anionic hopping properties of the ring opening product. Treatment of the ring opening product with base results in a facile phosphate hopping followed by a selective thiolate 3-exo-trig instead of a 5-exo-tet cyclization.

AB - Presented in this Letter is a mild new method to stereoselectively ring open 1,1-disubstituted vinyl oxiranes using dialkyl dithiophosphate nucleophiles. This new reaction proceeds in toluene at room temperature to afford tri- and tetrasubstituted allylic alcohols with high Z-selectivity. The syn relationship between the alcohol and the newly incorporated dithiophosphate moiety presented an opportunity to evaluate the anionic hopping properties of the ring opening product. Treatment of the ring opening product with base results in a facile phosphate hopping followed by a selective thiolate 3-exo-trig instead of a 5-exo-tet cyclization.

KW - Dithiophosphoric acid

KW - Regioselective

KW - Ring opening

KW - Vinyl oxirane

KW - Z-Selective

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