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

doi:10.1039/c6ob01980c

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

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

4 Citations (Scopus)

Abstract

The fluorous alkenes H₂CCHR_fn (R_fn = (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, R_f8, 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(CHCHR_fn)_m are detected. Thirteen representative examples are hydrogenated (Pd/C, balloon pressure H₂), giving Ar(CH₂CH₂R_fn)_m (92% average isolated yield).

Original language	English
Pages (from-to)	10058-10069
Number of pages	12
Journal	Organic and Biomolecular Chemistry
Volume	14
Issue number	42
DOIs	https://doi.org/10.1039/c6ob01980c
Publication status	Published - 2016
Externally published	Yes

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@article{362cfe586ca14c989422bf6021444ef5,

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.}",

note = "Publisher Copyright: {\textcopyright} 2016 The Royal Society of Chemistry.",

year = "2016",

doi = "10.1039/c6ob01980c",

language = "English",

volume = "14",

pages = "10058--10069",

journal = "Organic and Biomolecular Chemistry",

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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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U2 - 10.1039/c6ob01980c

DO - 10.1039/c6ob01980c

M3 - Article

AN - SCOPUS:84992694355

SN - 1477-0520

VL - 14

SP - 10058

EP - 10069

JO - Organic and Biomolecular Chemistry

JF - Organic and Biomolecular Chemistry

IS - 42

ER -

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

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