Application of amberlite IRA-400 (basic) as a base in heck reaction

Article abstract of DOI:10.1081/SCC-120015763

Amberlite IRA-400 (basic) has been used as a base in the Heck reaction and the generated quarternary ammonium salt might also be assisting in the reaction. The reaction is clean, simple and yields are high. The resin can be regenerated, recycled and the work-up procedure becomes simple compared to other bases used.

Full text of DOI:10.1081/SCC-120015763

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Application of Amberlite IRA-400 (Basic) as a Base in
Heck Reaction
S. B. Solabannavar a , V. B. Helavi a , U. V. Desai a & R. B. Mane a
a Department of Chemistry , Shivaji University , Kolhapur, India
Published online: 17 Aug 2006.
To cite this article: S. B. Solabannavar , V. B. Helavi , U. V. Desai & R. B. Mane (2003) Application of Amberlite IRA-400
(Basic) as a Base in Heck Reaction, Synthetic Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 33:3, 361-365, DOI: 10.1081/SCC-120015763
To link to this article: http://dx.doi.org/10.1081/SCC-120015763
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SYNTHETIC COMMUNICATIONSÕ
Vol. 33, No. 3, pp. 361–365, 2003
Application of Amberlite IRA-400 (Basic)
as a Base in Heck Reactiony
S. B. Solabannavar, V. B. Helavi, U. V. Desai,
*
and R. B. Mane
Department of Chemistry, Shivaji University,
Kolhapur, India
ABSTRACT
Amberlite IRA-400 (basic) has been used as a base in the Heck
reaction and the generated quarternary ammonium salt might also
be assisting in the reaction. The reaction is clean, simple and yields
are high. The resin can be regenerated, recycled and the work-up
procedure becomes simple compared to other bases used.
Palladiumcatalyzed olefin arylation/alkenylation developed primar-
ily by Heck,[1] is a well established method for the coupling of activated
olefins with aromatic/vinylic halides.[2] A base is generally added to the
Heck reaction[3] to regenerate Pd(o) from‘HPdx’ by neutralization of Hx.
yDedicated to the memory of Late Dr. Nitiraj R. Mane.
*Correspondence: R. B. Mane, Department of Chemistry, Shivaji University,
Kolhapur-416 004, India; E-mail: rbmane@yahoo.co.in.
361
DOI: 10.1081/SCC-120015763
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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362
Solabannavar et al.
In the Heck reaction cycle, after the migratory insertion comes the step in
which Pd(o) is released by PdH elimination to give alkene.
The termination occurs by nucleophilic attack at Pd, which either by
nucleophilic substitution or by reductive elimination of co-ordinated
nucleophile leads to the release of Pd(o). If PdH is not scavenged fast
by base, the readdition to the double bond may occur.
Trialkyl amines, carbonates, bicarbonates, acetates, potassium phos-
phate, alkoxides, hydroxides have been used as bases in Heck reaction.[4]
We report here the application of amberlite IRA-400 (basic) as a base in
the Heck reaction.
The reactions of aryl halides with olefins using palladiumacetate,
amberlite IRA-400 (basic) resin in DMF have been carried out in high
yields and purity (Table 1). The products at 2, 3 and 6 are important
intermediates for the synthesis of natural products prepared earlier by
multistep sequences. The Heck reaction with sorbic acid is interesting and
yields ꢀ-substitution product. The amberlite resin acts as a base and is
converted into the quaternary ammonium iodide which might also be
assisting the Heck reaction. There are reports in the literature[4,5] that
quaternary ammonium salts can effect the reduction of Pd(II) to Pd(o)
and thus stabilize palladiumcatalyst, leading to acceleration of the Heck
reaction. Thus the use of amberlite IRA-400 (basic) serves dual purpose
in assisting the Heck reaction.
The reaction is clean, simple and the resin can be regenerated and
recycled. The work-up procedure becomes simple compared to other
bases used.
GENERAL PROCEDURE
A mixture of palladium acetate (45 mg, 0.2 m mol), aryl halide
( p-iodotoluene/p-iodo anisole, 20 m mol), olefinic compound (25 m
mole) and amberlite IRA-400 (basic) 2 g in dry DMF (6 mL) was stirred
at 80ꢀC for 2 to 8 h. It was cooled and filtered to remove resin which was
washed with ether. The organic layer was diluted with water and
extracted with ether. The ether layer was washed with water and dried
over anhydrous sodiumsulphate. Removal of ether furnished the solid
products which were purified by recrystallization using suitable solvent
and liquids were purified by passing through chromatography column
(silica gel, pet. ether).

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Amberlite IRA-400 as Base in Heck Reaction
363

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364
Solabannavar et al.
Spectral Data for the Unknown Compounds
3-(4-Methyl-phenyl) 2-butenoic acid (2): IR: 1674 cmÀ1. PMR
[CDCl3]; ꢀ 2.35 (3H, s, Ar-CH3), 2.59 (3H, s, vinylic-CH3), 6.17 (1H, s,
vinylic-H), 7.20 (2H, d, J ¼ 8 Hz, Ar-H), 7.41 (2H, d, J ¼ 8 Hz, Ar-H).
MS (70 eV) m/e 176 (Mþ).
Methyl-3-(4-methyl-phenyl crotonate (6): IR: 1716 cmÀ1. PMR
(CDCl3): ꢀ 2.35 (3H, s, Ar-CH3), 2.56 (3H, s, vinylic-CH3), 3.74 (3H, s,
OCH3), 6.13 (1H, s, vinylic-H), 7.14 (2H, d, J ¼ 8 Hz, Ar-H), 7.39 (2H, d,
J ¼ 8 Hz, Ar-H). MS (70 eV) m/e 190 (Mþ).
Methyl-3-(4-methyl-phenyl) isobutyl crotonate (8): IR: 1713,
1628 cmÀ1. PMR (CDCl3): ꢀ 0.99 (6H, d, J ¼ 7 Hz, gem-dimethyl), 2.00
(1H, m, J ¼ 7 Hz, methine-H), 2.38 (3H, s, Ar-CH3), 2.58 (3H, s, vinylic-
CH3), 3.95 (2H, d, J ¼ 7 Hz,–O–CH2–), 6.16 (1H, bs, vinylic-H), 7.20 (2H,
d, J ¼ 8 Hz, Ar-H, ortho to methyl), 7.41 (2H, d, J ¼ 8 Hz, Ar-H, meta to
methyl). MS (70 eV) m/e 232 (Mþ).
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Nolley, J.P. J. Org. Chem. 1972, 14, 2320.
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Amberlite IRA-400 as Base in Heck Reaction
365
1423; (o) Gibson, S.E.; Middleton, R.J. Contemp. Org. Synth. 1996,
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Received in the Netherlands January 14, 2002

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