Multigramme synthesis and asymmetric dihydroxylation of a 4-fluorobut-2E-enoate

J A B Laurenson, J A Parkinson, J M Percy, G Rinaudo, R Roig

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Esters of crotonic acid were brominated on a multigramme scale using a free radical procedure. A phase transfer catalysed fluorination transformed these species to the 4-fluorobut-2E-enoates reproducibly and at scale (48–53%, ca. 300 mmol). Asymmetric dihydroxylation reactions were then used to transform the butenoate, ultimately into all four diastereoisomers of a versatile fluorinated
C4 building block at high enantiomeric-enrichment. The (DHQ)2AQN and (DHQD)2AQN ligands described by Sharpless were the most effective. The development and optimisation of a new and facile method for the determination of ee is also described; 19F{1H} spectra recorded in d-chloroform/diisopropyl tartrate showed distinct baseline separated signals for different enantiomers.
LanguageEnglish
Pages2660–2668
Number of pages9
JournalBeilstein Journal of Organic Chemistry
Volume9
DOIs
Publication statusPublished - 26 Nov 2013

Fingerprint

Fluorination
Enantiomers
Chloroform
Free Radicals
Esters
Ligands
tartaric acid
crotonic acid

Keywords

  • asymmetric
  • dihydroxylation
  • ee determination
  • fluorination
  • fluorosugars
  • organo-fluorine

Cite this

Laurenson, J A B ; Parkinson, J A ; Percy, J M ; Rinaudo, G ; Roig, R. / Multigramme synthesis and asymmetric dihydroxylation of a 4-fluorobut-2E-enoate. In: Beilstein Journal of Organic Chemistry . 2013 ; Vol. 9. pp. 2660–2668.
@article{6d890a86e1324defaf4cee4f2e9a1c15,
title = "Multigramme synthesis and asymmetric dihydroxylation of a 4-fluorobut-2E-enoate",
abstract = "Esters of crotonic acid were brominated on a multigramme scale using a free radical procedure. A phase transfer catalysed fluorination transformed these species to the 4-fluorobut-2E-enoates reproducibly and at scale (48–53{\%}, ca. 300 mmol). Asymmetric dihydroxylation reactions were then used to transform the butenoate, ultimately into all four diastereoisomers of a versatile fluorinatedC4 building block at high enantiomeric-enrichment. The (DHQ)2AQN and (DHQD)2AQN ligands described by Sharpless were the most effective. The development and optimisation of a new and facile method for the determination of ee is also described; 19F{1H} spectra recorded in d-chloroform/diisopropyl tartrate showed distinct baseline separated signals for different enantiomers.",
keywords = "asymmetric, dihydroxylation, ee determination, fluorination, fluorosugars, organo-fluorine",
author = "Laurenson, {J A B} and Parkinson, {J A} and Percy, {J M} and G Rinaudo and R Roig",
year = "2013",
month = "11",
day = "26",
doi = "10.3762/bjoc.9.301",
language = "English",
volume = "9",
pages = "2660–2668",
journal = "Beilstein Journal of Organic Chemistry",
issn = "1860-5397",

}

Multigramme synthesis and asymmetric dihydroxylation of a 4-fluorobut-2E-enoate. / Laurenson, J A B; Parkinson, J A; Percy, J M; Rinaudo, G; Roig, R.

In: Beilstein Journal of Organic Chemistry , Vol. 9, 26.11.2013, p. 2660–2668.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Multigramme synthesis and asymmetric dihydroxylation of a 4-fluorobut-2E-enoate

AU - Laurenson, J A B

AU - Parkinson, J A

AU - Percy, J M

AU - Rinaudo, G

AU - Roig, R

PY - 2013/11/26

Y1 - 2013/11/26

N2 - Esters of crotonic acid were brominated on a multigramme scale using a free radical procedure. A phase transfer catalysed fluorination transformed these species to the 4-fluorobut-2E-enoates reproducibly and at scale (48–53%, ca. 300 mmol). Asymmetric dihydroxylation reactions were then used to transform the butenoate, ultimately into all four diastereoisomers of a versatile fluorinatedC4 building block at high enantiomeric-enrichment. The (DHQ)2AQN and (DHQD)2AQN ligands described by Sharpless were the most effective. The development and optimisation of a new and facile method for the determination of ee is also described; 19F{1H} spectra recorded in d-chloroform/diisopropyl tartrate showed distinct baseline separated signals for different enantiomers.

AB - Esters of crotonic acid were brominated on a multigramme scale using a free radical procedure. A phase transfer catalysed fluorination transformed these species to the 4-fluorobut-2E-enoates reproducibly and at scale (48–53%, ca. 300 mmol). Asymmetric dihydroxylation reactions were then used to transform the butenoate, ultimately into all four diastereoisomers of a versatile fluorinatedC4 building block at high enantiomeric-enrichment. The (DHQ)2AQN and (DHQD)2AQN ligands described by Sharpless were the most effective. The development and optimisation of a new and facile method for the determination of ee is also described; 19F{1H} spectra recorded in d-chloroform/diisopropyl tartrate showed distinct baseline separated signals for different enantiomers.

KW - asymmetric

KW - dihydroxylation

KW - ee determination

KW - fluorination

KW - fluorosugars

KW - organo-fluorine

UR - http://www.beilstein-institut.de/en/journals

U2 - 10.3762/bjoc.9.301

DO - 10.3762/bjoc.9.301

M3 - Article

VL - 9

SP - 2660

EP - 2668

JO - Beilstein Journal of Organic Chemistry

T2 - Beilstein Journal of Organic Chemistry

JF - Beilstein Journal of Organic Chemistry

SN - 1860-5397

ER -