The effect of the carbon ligand on the reaction of organozinc reagents in the synthesis of substituted 2,5-dihydrofurans: A rare example of an uncatalysed allylic-substitution reaction involving alkyl zinc halides

Mark Woods, Nuno Monteiro, Geneviève Balme

Research output: Contribution to journalArticle

19 Citations (Scopus)

Abstract

Organozinc halides derived from Grignard reagents behave differently in their reaction with ethyl (±)-(2RS,3SR)-tetrahydro-4-methylene-2-phenyl-3- (phenylsulfonyl)furan-3-carboxylate (3) according to the hybridisation of the carbon ligand. During the development of short multi-component reactions for the synthesis of diverse functionalized ethyl 2,5-dihydrofuran-3-carboxylates it was discovered that aryl and vinyl zinc halides undergo clean reaction with 3 in the presence of Pd(PPh3)4. In contrast, when alkyl zinc halides are reacted with 3 in the presence of Pd(PPh3)4, reductive desulfonation of 3 is observed. Remarkably, in the absence of a transition metal catalyst, the allylic substitution of 3 with alkyl zinc halides proceeds cleanly and in moderate to good yield.

Original languageEnglish (US)
Pages (from-to)1711-1718
Number of pages8
JournalEuropean Journal of Organic Chemistry
Issue number9
StatePublished - May 2000
Externally publishedYes

Fingerprint

halides
reagents
Zinc
Substitution reactions
Carbon
zinc
substitutes
Ligands
ligands
carbon
synthesis
carboxylates
Transition metals
furans
methylene
Catalysts
transition metals
catalysts
2,5-dihydrofuran
furan

Keywords

  • Catalysts
  • Heterocycles
  • Palladium
  • Sulfur
  • Zinc

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

@article{e114f63d2b12437dab244298fee9c265,
title = "The effect of the carbon ligand on the reaction of organozinc reagents in the synthesis of substituted 2,5-dihydrofurans: A rare example of an uncatalysed allylic-substitution reaction involving alkyl zinc halides",
abstract = "Organozinc halides derived from Grignard reagents behave differently in their reaction with ethyl (±)-(2RS,3SR)-tetrahydro-4-methylene-2-phenyl-3- (phenylsulfonyl)furan-3-carboxylate (3) according to the hybridisation of the carbon ligand. During the development of short multi-component reactions for the synthesis of diverse functionalized ethyl 2,5-dihydrofuran-3-carboxylates it was discovered that aryl and vinyl zinc halides undergo clean reaction with 3 in the presence of Pd(PPh3)4. In contrast, when alkyl zinc halides are reacted with 3 in the presence of Pd(PPh3)4, reductive desulfonation of 3 is observed. Remarkably, in the absence of a transition metal catalyst, the allylic substitution of 3 with alkyl zinc halides proceeds cleanly and in moderate to good yield.",
keywords = "Catalysts, Heterocycles, Palladium, Sulfur, Zinc",
author = "Mark Woods and Nuno Monteiro and Genevi{\`e}ve Balme",
year = "2000",
month = "5",
language = "English (US)",
pages = "1711--1718",
journal = "Annalen der Pharmacie",
issn = "0075-4617",
publisher = "Wiley-VCH Verlag",
number = "9",

}

TY - JOUR

T1 - The effect of the carbon ligand on the reaction of organozinc reagents in the synthesis of substituted 2,5-dihydrofurans

T2 - A rare example of an uncatalysed allylic-substitution reaction involving alkyl zinc halides

AU - Woods, Mark

AU - Monteiro, Nuno

AU - Balme, Geneviève

PY - 2000/5

Y1 - 2000/5

N2 - Organozinc halides derived from Grignard reagents behave differently in their reaction with ethyl (±)-(2RS,3SR)-tetrahydro-4-methylene-2-phenyl-3- (phenylsulfonyl)furan-3-carboxylate (3) according to the hybridisation of the carbon ligand. During the development of short multi-component reactions for the synthesis of diverse functionalized ethyl 2,5-dihydrofuran-3-carboxylates it was discovered that aryl and vinyl zinc halides undergo clean reaction with 3 in the presence of Pd(PPh3)4. In contrast, when alkyl zinc halides are reacted with 3 in the presence of Pd(PPh3)4, reductive desulfonation of 3 is observed. Remarkably, in the absence of a transition metal catalyst, the allylic substitution of 3 with alkyl zinc halides proceeds cleanly and in moderate to good yield.

AB - Organozinc halides derived from Grignard reagents behave differently in their reaction with ethyl (±)-(2RS,3SR)-tetrahydro-4-methylene-2-phenyl-3- (phenylsulfonyl)furan-3-carboxylate (3) according to the hybridisation of the carbon ligand. During the development of short multi-component reactions for the synthesis of diverse functionalized ethyl 2,5-dihydrofuran-3-carboxylates it was discovered that aryl and vinyl zinc halides undergo clean reaction with 3 in the presence of Pd(PPh3)4. In contrast, when alkyl zinc halides are reacted with 3 in the presence of Pd(PPh3)4, reductive desulfonation of 3 is observed. Remarkably, in the absence of a transition metal catalyst, the allylic substitution of 3 with alkyl zinc halides proceeds cleanly and in moderate to good yield.

KW - Catalysts

KW - Heterocycles

KW - Palladium

KW - Sulfur

KW - Zinc

UR - http://www.scopus.com/inward/record.url?scp=0034078740&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0034078740&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0034078740

SP - 1711

EP - 1718

JO - Annalen der Pharmacie

JF - Annalen der Pharmacie

SN - 0075-4617

IS - 9

ER -