Convenient protocols for Mizoroki-Heck reactions of aromatic bromides and polybromides with fluorous alkenes of the formula H2CCH(CF2)n-1CF3 (n = 8, 10)

Haw Lih Su, Janos Balogh, Mohammed Al-Hashimi, Dave G. Seapy, Hassan S. Bazzi, John A. Gladysz

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2 Citations (Scopus)

Abstract

The fluorous alkenes H2CCHRfn (Rfn = (CF2)n-1CF3; n = 8, 10) undergo the Mizoroki-Heck reaction with a variety of aromatic monobromides and polybromides such as 1,3- and 1,4-C6H4Br2, 1,3,5-C6H3Br3, 1,3,5-C6H3Br2Cl, 1,4-XC6H4Br (X = CF3, Rf8, COCH3, CN, 1,4-OC6H4Br), 1,2-O2NC6H4Br, 5-bromoisoquinoline, 5-bromopyrimidine, 3-bromo-5-methoxypyridine, and 3,5-dibromopyridine (sixteen examples, 78% average isolated yield). Typically, 1.2-2.4 equiv. of alkene are employed per Ar-Br bond, together with Pd(OAc)2 catalyst (4-5 mol%/Ar-Br bond), n-Bu4N+ Br- (0.8-1.0 equiv./Ar-Br bond), NaOAc (1.2-2.4 equiv./Ar-Br bond), and 3 : 1 w/w DMF/THF as solvent (120 °C). No effort is necessary to exclude air or moisture, and reactions may be conducted on >10 g scales. Only E isomers of the products Ar(CHCHRfn)m are detected. Thirteen representative examples are hydrogenated (Pd/C, balloon pressure H2), giving Ar(CH2CH2Rfn)m (92% average isolated yield).

Original languageEnglish
Pages (from-to)10058-10069
Number of pages12
JournalOrganic and Biomolecular Chemistry
Volume14
Issue number42
DOIs
Publication statusPublished - 2016

Fingerprint

Alkenes
Bromides
alkenes
bromides
Balloons
balloons
moisture
Isomers
Moisture
isomers
Air
Pressure
catalysts
Catalysts
air
products
palladium(II) acetate
3,5-dibromopyridine
5-bromopyrimidine

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

@article{34ed35d236644e1f89b1c0cf83ec0a3b,
title = "Convenient protocols for Mizoroki-Heck reactions of aromatic bromides and polybromides with fluorous alkenes of the formula H2CCH(CF2)n-1CF3 (n = 8, 10)",
abstract = "The fluorous alkenes H2CCHRfn (Rfn = (CF2)n-1CF3; n = 8, 10) undergo the Mizoroki-Heck reaction with a variety of aromatic monobromides and polybromides such as 1,3- and 1,4-C6H4Br2, 1,3,5-C6H3Br3, 1,3,5-C6H3Br2Cl, 1,4-XC6H4Br (X = CF3, Rf8, COCH3, CN, 1,4-OC6H4Br), 1,2-O2NC6H4Br, 5-bromoisoquinoline, 5-bromopyrimidine, 3-bromo-5-methoxypyridine, and 3,5-dibromopyridine (sixteen examples, 78{\%} average isolated yield). Typically, 1.2-2.4 equiv. of alkene are employed per Ar-Br bond, together with Pd(OAc)2 catalyst (4-5 mol{\%}/Ar-Br bond), n-Bu4N+ Br- (0.8-1.0 equiv./Ar-Br bond), NaOAc (1.2-2.4 equiv./Ar-Br bond), and 3 : 1 w/w DMF/THF as solvent (120 °C). No effort is necessary to exclude air or moisture, and reactions may be conducted on >10 g scales. Only E isomers of the products Ar(CHCHRfn)m are detected. Thirteen representative examples are hydrogenated (Pd/C, balloon pressure H2), giving Ar(CH2CH2Rfn)m (92{\%} average isolated yield).",
author = "Su, {Haw Lih} and Janos Balogh and Mohammed Al-Hashimi and Seapy, {Dave G.} and Bazzi, {Hassan S.} and Gladysz, {John A.}",
year = "2016",
doi = "10.1039/c6ob01980c",
language = "English",
volume = "14",
pages = "10058--10069",
journal = "Organic and Biomolecular Chemistry",
issn = "1477-0520",
publisher = "Royal Society of Chemistry",
number = "42",

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TY - JOUR

T1 - Convenient protocols for Mizoroki-Heck reactions of aromatic bromides and polybromides with fluorous alkenes of the formula H2CCH(CF2)n-1CF3 (n = 8, 10)

AU - Su, Haw Lih

AU - Balogh, Janos

AU - Al-Hashimi, Mohammed

AU - Seapy, Dave G.

AU - Bazzi, Hassan S.

AU - Gladysz, John A.

PY - 2016

Y1 - 2016

N2 - The fluorous alkenes H2CCHRfn (Rfn = (CF2)n-1CF3; n = 8, 10) undergo the Mizoroki-Heck reaction with a variety of aromatic monobromides and polybromides such as 1,3- and 1,4-C6H4Br2, 1,3,5-C6H3Br3, 1,3,5-C6H3Br2Cl, 1,4-XC6H4Br (X = CF3, Rf8, COCH3, CN, 1,4-OC6H4Br), 1,2-O2NC6H4Br, 5-bromoisoquinoline, 5-bromopyrimidine, 3-bromo-5-methoxypyridine, and 3,5-dibromopyridine (sixteen examples, 78% average isolated yield). Typically, 1.2-2.4 equiv. of alkene are employed per Ar-Br bond, together with Pd(OAc)2 catalyst (4-5 mol%/Ar-Br bond), n-Bu4N+ Br- (0.8-1.0 equiv./Ar-Br bond), NaOAc (1.2-2.4 equiv./Ar-Br bond), and 3 : 1 w/w DMF/THF as solvent (120 °C). No effort is necessary to exclude air or moisture, and reactions may be conducted on >10 g scales. Only E isomers of the products Ar(CHCHRfn)m are detected. Thirteen representative examples are hydrogenated (Pd/C, balloon pressure H2), giving Ar(CH2CH2Rfn)m (92% average isolated yield).

AB - The fluorous alkenes H2CCHRfn (Rfn = (CF2)n-1CF3; n = 8, 10) undergo the Mizoroki-Heck reaction with a variety of aromatic monobromides and polybromides such as 1,3- and 1,4-C6H4Br2, 1,3,5-C6H3Br3, 1,3,5-C6H3Br2Cl, 1,4-XC6H4Br (X = CF3, Rf8, COCH3, CN, 1,4-OC6H4Br), 1,2-O2NC6H4Br, 5-bromoisoquinoline, 5-bromopyrimidine, 3-bromo-5-methoxypyridine, and 3,5-dibromopyridine (sixteen examples, 78% average isolated yield). Typically, 1.2-2.4 equiv. of alkene are employed per Ar-Br bond, together with Pd(OAc)2 catalyst (4-5 mol%/Ar-Br bond), n-Bu4N+ Br- (0.8-1.0 equiv./Ar-Br bond), NaOAc (1.2-2.4 equiv./Ar-Br bond), and 3 : 1 w/w DMF/THF as solvent (120 °C). No effort is necessary to exclude air or moisture, and reactions may be conducted on >10 g scales. Only E isomers of the products Ar(CHCHRfn)m are detected. Thirteen representative examples are hydrogenated (Pd/C, balloon pressure H2), giving Ar(CH2CH2Rfn)m (92% average isolated yield).

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DO - 10.1039/c6ob01980c

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JO - Organic and Biomolecular Chemistry

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SN - 1477-0520

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