Allylation of esters promoted by metallic dysprosium in the presence of mercuric chloride

Article abstract of DOI:10.1081/SCC-120006467

In the presence of mercuric chloride, the reactions of esters with allyl bromide and metallic dysprosium in anhydrous THF give diallyl alkyl carbinols in good yields. When γ-butyrolactone is used as the substrate, the corresponding product is 4-allyl-6-heptene-1, 4-diol.

Full text of DOI:10.1081/SCC-120006467

Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic
Chemistry
ISSN: 0039-7911 (Print) 1532-2432 (Online) Journal homepage: http://www.tandfonline.com/loi/lsyc20
ALLYLATION OF ESTERS PROMOTED BY METALLIC
DYSPROSIUM IN THE PRESENCE OF MERCURIC
CHLORIDE
Yu Jia , Mingfu Zhang , Fenggang Tao & Jingyao Zhou
To cite this article: Yu Jia , Mingfu Zhang , Fenggang Tao & Jingyao Zhou (2002) ALLYLATION OF
ESTERS PROMOTED BY METALLIC DYSPROSIUM IN THE PRESENCE OF MERCURIC CHLORIDE,
Synthetic Communications, 32:18, 2829-2835, DOI: 10.1081/SCC-120006467
To link to this article: http://dx.doi.org/10.1081/SCC-120006467
Published online: 18 Oct 2011.
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SYNTHETIC COMMUNICATIONS
Vol. 32, No. 18, pp. 2829–2835, 2002
ALLYLATION OF ESTERS PROMOTED
BY METALLIC DYSPROSIUM IN THE
PRESENCE OF MERCURIC CHLORIDE
*
Yu Jia, Mingfu Zhang, Fenggang Tao,
and Jingyao Zhou
Department of Chemistry, Fudan University,
Shanghai 200433, P.R. China
ABSTRACT
In the presence of mercuric chloride, the reactions of esters
with allyl bromide and metallic dysprosium in anhydrous
THF give diallyl alkyl carbinols in good yields. When
g-butyrolactone is used as the substrate, the corresponding
product is 4-allyl-6-heptene-1, 4-diol.
Key Words: Metallic dysprosium; Allylation
With high coordinative activity and contribution of f orbitals to ꢀ
and ꢁ bonds, lanthanide metals exhibit unique reactivity in organic reac-
tions and possess intriguing potential as reagents and catalysts.[1]
Therefore their use for synthetic purposes is promising. In recent years,
more and more attention has been paid to the utilization of lanthanides in
organic synthesis. Some of the lanthanides, such as Ce,[2] Sm,[3] Yb,[4] etc.,
*Corresponding author. E-mail: yujia@fudan.edu.com
2829
DOI: 10.1081/SCC-120006467
Copyright & 2002 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
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2830
JIA ET AL.
have been successfully investigated, and many interesting synthetic
procedures have been developed. However, to our best knowledge no
report other than our own,[5] has been found about the use of
metallic dysprosium in organic reactions involving carbon–carbon bond
formation.
Recently, we reported that metallic dysprosium is effective in promot-
ing the allylation of ketones in the presence of mercuric chloride.[5] As the
continuing study, we report herein the allylation of esters promoted by
dysprosium metal, which affords the corresponding diallyl alkyl carbinols
in good yields.
Diallyl alkyl carbinols are intermediates of great synthetic potential,
since they can be used to synthesize a variety of compounds such as hydro-
xyl lactone,[6] polyacrylamide gel,[7] and some natural products.[8] They are
normally prepared by the reactions of esters with allyl organometallic (such
as Mg, Zn, etc.) reagents or allyl boranes.[9] We report here a new method to
synthesize them by allylation of esters promoted by metallic dysprosium in
the presence of mercuric chloride.
First, we carried out the reaction of ethyl benzoate with allyl bro-
mide and dysprosium powder in anhydrous THF, and no products were
found by TLC after 12 h (Table 1, Entry 1). When a catalytic amount of
Lewis acid BF3ꢀEt2O was added, which enhanced the electrophilic activity
of ester through coordination, the reaction gave the corresponding
4-phenyl-1,6-heptadiene-4-ol in low yield (Entry 2). When a catalytic
amount of HgCl2 was added, the yield of 4-phenyl-1,6-heptadiene-4-ol
increased considerably (Entry 3). Evidently the catalytic effect of HgCl2
is better than that of BF3ꢀEt2O. As mentioned in our previous paper,[5] the
mercuric chloride, which reacted with the metallic dysprosium to form the
highly reactive dysprosium amalgam, functioned in this reaction as an
initiator.
In the presence of catalytic amount of HgCl2, allyl bromide and
metallic dysprosium could react with aromatic and aliphatic esters to give
the corresponding diallyl alkyl carbinols in good yields, as shown in
Scheme 1.
When g-butyrolactone was used as the substrate, the corresponding
product is 4-allyl-6-heptene-1,4-diol (Scheme 2).
A number of aromatic and aliphatic esters were used in this reaction,
and the results are summarized in Table 1.
In our previous work,[5] we found that the addition of sodium iodide
could increase the yield of allylation product considerably in the reaction of
ketone with allyl bromide and dysprosium powder. But when one equivalent
of sodium iodide was added in this reaction (Entries 6–8), unexpectedly the
yield of diallyl alkyl carbinol was not increased.

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METALLIC DYSPROSIUM
2831
Table 1. The Allylation of Esters Promoted by Metallic Dysprosium
Substrate
Molar Ratioa
(RCOOR1 /
Allyl halide/
Yielde
(%)
Entry
Esters
Dy)
Conditions
r.t.(12 h)
Product
1
2
3
C6H5CO2Et
C6H5CO2Et
C6H5CO2Et
1.0/2.5/2.5b
1.0/2.0/2.5c
1.0/2.5/2.5
1.0/2.5/2.5
1.0/2.5/2.5
1.0/2.5/2.5d
1.0/2.5/2.5d
1.0/2.5/2.5d
1.0/4.0/4.0
1.0/4.0/4.0
1.0/4.0/4.0
1.0/4.0/4.0
1.0/4.0/4.0
–
–
r.t.(24 h)
1a
1a
1b
1c
1a
1b
1c
1d
1e
1f
1g
2
16f
73
87
81
70
85
80
74
84
73
59
62
0ꢁC(2 h), r.t.(4 h)
0ꢁC(2 h), r.t.(4 h)
0ꢁC(2 h), r.t.(4 h)
0ꢁC(2 h), r.t.(4 h)
0ꢁC(2 h), r.t.(4 h)
0ꢁC(2 h), r.t.(4 h)
0ꢁC(2 h), r.t.(4 h)
0ꢁC(2 h), r.t.(4 h)
0ꢁC(2 h), r.t.(4 h)
0ꢁC(2 h), r.t.(4 h)
0ꢁC(2 h), r.t.(4 h)
4
5
6
C6H5CH2CO2Me
m-ClC6H4CO2Et
C6H5CO2Et
7
8
9
C6H5CH2CO2Me
m-ClC6H4CO2Et
CH3CO2Et
10
11
12
13
CH3CH2CO2Et
CH3CH2CH2CO2Et
CH2¼C(CH3)CO2Et
g-Butyrolactone
aAll reactions of esters were carried out on a 2 mmol scale. Except in Entries 1 and 2,
a catalytic amount of HgCl2 was added in every other case.
bNo HgCl2 or BF3ÁEt2O was added.
cA catalytic amount of BF3ÁEt2O was added.
dOne molar eq. of NaIwas added.
1
eIsolated yields. The structures of all the products were confirmed by H NMR and
IR spectroscopy.
f75% of starting ethyl benzoate was recovered.
Scheme 1.
Scheme 2.

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2832
JIA ET AL.
Scheme 3.
This reaction is regioselective. An a,b-unsaturated ester (Entry 12)
afforded a 1,2-addition product selectively, and no 1,4-addition product
was found.
As shown in Scheme 3, the reactions of esters and crotyl bromide
promoted by metallic dysprosium only gave g-adduct products.
EXPERIMENTAL
Elemental analyses were performed by Perkin-Elmer 240C elemental
analyzer. Infrared Spectra were recorded on an AVVATAR 360 FT-IR
instrument. Nuclear magnetic resonance was recorded on a JNM-PMX 60
SI(60 MHz, JEOL) or a BRUKER (300 MHz).
The metallic dysprosium used in the reactions was prepared from a
dysprosium ingot by carefully scraping with a rasp. THF was treated with
sodium and distilled before use. Ethyl acetate and petroleum ether used in
the flash column chromatography were distilled before use.
Reaction of Esters with Allyl Bromide and Metallic
Dysprosium Powder
A mixture of ester (2 mmol), allyl bromide (5 mmol), dysprosium
powder (5 mmol) (or 2 mmol of ester, 8 mmol of allyl bromide and
8 mmol of dysprosium powder), mercuric chloride (150 mg) and anhydrous
THF (15 mL) was stirred at 0ꢁC for 2 h and then at room temperature for
4 h. Then the reaction mixture was treated with 10 mL of saturated aqueous
NH4Cl and extracted with ether. The combined organic extracts were dried
over magnesium sulfate. After the evaporation of ether, the residue was

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METALLIC DYSPROSIUM
2833
purified by flash column chromatography, a mixture of petroleum ether and
ethyl acetate being used as the elution solvent, and from which the products
were isolated.
4-Phenyl-1,6-heptadiene-4-ol[3e] (1a): IR (neat) 3500 (br, O–H), 1630
1
(s, C¼C), 910 (s, CH¼CH2) cmꢂ1. H NMR(CDCl3, TMS) ꢂ 2.21 (s, 1H,
OH), 2.48–2.74 (m, 4H, 2 ꢃ CH2CH¼CH2), 5.06–5.85 (m, 6H,
2 ꢃ CH¼CH2), 7.21–7.42 (m, 5H, C6H5).
4-Benzyl-1,6-heptadiene-4-ol[3e] (1b): IR (neat) 3450 (br, O–H), 1630
1
(s, C¼C), 905 (s, CH¼CH2) cmꢂ1. H NMR(CCl4, HMDS) ꢂ 1.37 (s, 1H,
OH), 2.07 (d, 4H, 2 ꢃ CH2CH¼CH2), 2.57 (s, 2H, C6H5CH2), 4.67–6.13 (m,
6H, 2 ꢃ CH¼CH2), 6.93–7.17 (m, 5H, C6H5).
m-Chlorophenyl-1,6-heptadiene-4-ol[3e] (1c): IR (neat) 3530 (br, O–H),
1
1630 (s, C¼C), 910 (s, CH¼CH2) cmꢂ1. H NMR(CCl4, HMDS) ꢂ 1.97 (s,
1H, OH), 2.30–2.53 (m, 4H, 2 ꢃ CH2CH¼CH2), 4.67–5.87 (m, 6H,
2 ꢃ CH¼CH2), 6.93–7.27 (m, 4H, C6H4).
4-Methyl-1,6-heptadiene-4-ol[3e] (1d): IR (neat) 3350 (br, O–H), 1630
1
(s, C¼C), 910 (s, CH¼CH2) cmꢂ1. H NMR(CCl4, HMDS) ꢂ 1.03 (s, 3H,
CH3), 1.43 (s, 1H, OH), 2.10 (d, 4H, 2 ꢃ CH2CH¼CH2), 4.70–6.10 (m, 6H,
2 ꢃ CH¼CH2).
4-Ethyl-1,6-heptadiene-4-ol[3e] (1e): IR (neat) 3350 (br, O–H), 1630
1
(s, C¼C), 910 (s, CH¼CH2) cmꢂ1. H NMR(CCl4, HMDS) ꢂ 0.70–1.03 (t,
3H, CH2CH3), 1.33 (q, 2H, CH2CH3), 1.57 (s, 1H, OH), 2.10 (d, 4H,
2 ꢃ CH2CH¼CH2), 4.70–6.07 (m, 6H, 2 ꢃ CH¼CH2).
4-n-Propyl-1,6-heptadiene-4-ol[10] (1f): IR (neat) 3350 (br, O–H), 1630
1
(s, C¼C), 910 (s, CH¼CH2) cmꢂ1. H NMR(CCl4, HMDS) ꢂ 0.73–1.40 (m,
7H, CH2CH2CH3), 1.10 (s, 1H, OH), 2.10 (d, 4H, 2 ꢃ CH2CH¼CH2),
4.67–6.0 (m, 6H, 2 ꢃ CH¼CH2).
4-(1-Methylvinyl)-1,6-heptadiene-4-ol[11] (1 g): IR (neat) 3450 (br, O–H),
1630 (s, C¼C), 900 (s, C¼CH2) cmꢂ1. 1H NMR(CCl4, HMDS) ꢂ 1.57 (s, 1H,
OH), 1.63 (s, 3H, CH3), 2.20 (d, 4H, 2 ꢃ CH2CH¼CH2), 4.63–5.97 (m, 8H,
2 ꢃ CH¼CH2, C(CH3)¼CH2).
4-Allyl-6-heptene-1,4-diol[3e] (2): IR (neat) 3300 (br, O–H), 1630 (s,
1
C¼C), 905 (s, C¼CH2) cmꢂ1. H NMR(CCl4, HMDS) ꢂ 1.37–1.70 (m, 4H,
CH2CH2), 2.13 (d, 4H, 2 ꢃ CH2CH¼CH2), 3.47 (t, 2H, CH2OH), 3.90 (s,
2H, 2 ꢃ OH), 4.70–6.10 (m, 6H, 2 ꢃ CH¼CH2).
3,5-Dimethyl-4-Phenyl-1,6-heptadiene-4-ol (3): IR (neat) 3500 (br,
1
O–H), 1630 (s, C¼C), 910 (s, CH¼CH2) cmꢂ1. H NMR(CDCl3, HMDS)
ꢂ 0.70–1.00 (m, 6H, 2 ꢃ CH3), 1.50 (br, 1H, OH), 2.33–2.97 (m, 2H, 2 ꢃ
CHCH¼CH2), 4.67–6.00 (m, 6H, 2 ꢃ CH¼CH2), 7.00–7.30 (m, 5H, C6H5).
Anal. Calcd. for C15H20O: C, 83.28; H, 9.32. Found: C, 83.55; H, 9.30.
6-Methyl-4-(1-butene-3-yl)-7-heptene-1,4-diol (4): IR (neat) 3400 (br,
O–H), 1630 (s, C¼C), 910 (s, C¼CH2) cmꢂ1
.
1H NMR(CDCl3, TMS)

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2834
JIA ET AL.
ꢂ 0.97 (d, 6H, 2 ꢃ CH3), 1.37–1.70 (m, 4H, CH2CH2), 2.00–2.27 (m, 2H,
2 ꢃ CHCH¼CH2), 2.50 (br, 2H, 2 ꢃ OH), 3.47 (t, 2H, CH2OH), 4.67–6.10
(m, 6H, 2 ꢃ CH¼CH2). Anal. Calcd. for C12H22O2: C, 72.68; H, 11.18.
Found: C, 72.88; H, 11.03.
ACKNOWLEDGMENTS
We thank the National Natural Science Foundation of China (project
No. 29872008) for financial support.
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Received in the UK June 29, 2001