Telomerization of butadiene with L-arabinose and D-xylose in DMF: Selective formation of their monooctadienyl glycosides

Article abstract of DOI:10.1002/ejoc.200400064

Conditions to achieve the palladium-catalysed telomerization of butadiene with L-arabinose and D-xylose as telogens have been identified. With DMF as solvent, optimised ratios of substrate, reactants and catalytic system allowed the selective grafting of

Full text of DOI:10.1002/ejoc.200400064

FULL PAPER
Telomerization of Butadiene with
L
-Arabinose and -Xylose in DMF:
D
Selective Formation of their Monooctadienyl Glycosides
[a]
[a]
[a]
[a]
´
Boris Estrine, Sandrine Bouquillon, Francoise Henin,* and Jacques Muzart
¸
Keywords: Butadiene telomerization / Free pentoses / Palladium catalysis / Octadienyl pentosides
Conditions to achieve the palladium-catalysed telomeriz- lective grafting of one octadienyl chain onto the anomeric
ation of butadiene with
L-arabinose and
D-xylose as telogens
hydroxy group.
have been identified. With DMF as solvent, optimised ratios
of substrate, reactants and catalytic system allowed the se-
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2004)
Since its discovery in 1967[1] the palladium-catalysed telo- petes with the sugar as nucleophilic species.[7,8] The mecha-
merization of butadiene in the presence of alcohols or phen- nism of telomerization of butadiene with methanol, estab-
ols as nucleophiles has been extensively studied and applied lished in careful studies by several German teams,[12Ϫ14] has
to a variety of other nucleophiles.[2] The reaction constitutes been substantiated by DFT calculations.[15] The parameters
an elegant method by which to provide a large range of governing the regioselectivity of the linear or branched
functionalised compounds that can be used as building chain grafting are quite well controlled with nucleophiles
blocks for fine chemicals and for industrial such as methanol[13] or ammonia.[16] The proportion of
applications.[2Ϫ4] Thanks to the increasing importance of mono- or polysubstitution by the octadienyl chain has also
carbohydrates as cheap and renewable starting materials, been studied, starting from bifunctional active hydrogen
the use of these compounds as nucleophiles in telomeriz- compounds: a high selectivity towards monosubstituted lin-
ation is of great interest with regard to the production of ear telomer has, for example, been achieved from ethylene
biodegradable non-ionic surfactants.[5] A protected galac- glycol in biphasic systems[17] or by use of polymer-bound
tose was reported as the first carbohydrate derivative used palladium(0) complexes as catalysts.[18]
for telomerization with butadiene.[6] Later on, the subject
We were interested in the possibility of making the most
was studied in depth from both academic and industrial of pentoses, mainly -arabinose and -xylose, which are
perspectives, telomerization being carried out with free sug- now easily extracted from wheat straw and bran.[19] The
ars, mainly sucrose, but also glucose or its derivatives, and telomerization of butadiene with these carbohydrates would
the reaction being developed in organic (mainly 2-propanol constitute an attractive route by which to prepare mono-
mixtures)[7,8] or aqueous media.[9Ϫ11] The catalytic system ethers directly without the use of protection and deprotec-
was based on palladium [especially Pd(acac)2 or Pd(OAc)2] tion steps. Here we report the results of this study, having
associated with a phosphane that could be water-soluble if succeeded in obtaining good control over the monoether-
required.[9Ϫ11] Different variations of the reaction con- ification of the polyols by an octadienyl chain.
ditions were carried out, allowing high efficiency to be at-
tained,[8] but whatever the medium, the transformation gave
complex mixtures of polyethers in which the average degree
of etherification of hydroxy groups was difficult to control.
Results and Discussion
The best selectivity for the monooctadienyl ether of sucrose
was reported with the use of aqueous NaOH and with 2-
propanol as a co-solvent, the average degree of etherifi-
cation being 1.3.[10] However, the process described in aque-
ous NaOH was not compatible with reducing sugars such
as aldoses;[9,10] furthermore, an alcoholic co-solvent com-
The telomerization reaction was carried out in an auto-
clave (50 mL), with 1 g of -arabinose (1) or -xylose (2)
and an excess of butadiene. The reaction products
(Scheme 1) were analysed by GC/MS after peracetylation
of the mixture and subsequent distillation under vacuum to
separate the solvent and the butadiene dimers (1,3,7-octatri-
ene and 4-vinylcyclohexene) from the remaining sugar and
the sugar-derived products (see Exp. Sect.). These last were
first identified as mono- or polyethers by their mass spectra.
[a]
´
´
´
Unite Mixte de Recherche ‘‘Reactions Selectives et
´
Applications’’, CNRS Ϫ Universite de Reims Champagne-
Ardenne,
B. P. 1039, 51687 Reims Cedex 2, France
Fax: (internat.) ϩ 33-326913166
E-mail: francoise.henin@univ-reims.fr
2914
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejoc.200400064
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Telomerization of Butadiene with L-Arabinose and D-Xylose in DMF
FULL PAPER
either sugar was transformed, while the butadiene under-
went dimerisation (Entries 2, 3). As the results of telomeriz-
ation reactions can be improved by addition of base,[20,21]
we tested inorganic additives such as Na2CO3 and NaOH,
but without success. In contrast, addition of triethylamine
increased the degree of conversion of the sugar to over 50%,
and the selectivity for monoether formation was also im-
proved (Entries 4, 5). Consequently, different tertiary am-
ines were tested (Figure 1).
Scheme 1. Telomerization reaction of butadiene with -arabinose
and -xylose
Several tertiary amines Ϫ iPr2EtN, Et3N, iPr2MeN,
nPr3N, DABCO and iPr3N Ϫ provided a beneficial effect
in regard to the conversion of the arabinose, although only
iPr2EtN proved to be slightly superior to Et3N. In the pres-
ence of strong bases such as DBU or TMG (tetramethyl
guanidine) no improvement was observed. It clearly ap-
pears that there is no correlation between the strength of
the base and the conversion values. According to Beller,[22]
one possible role of added amines might be to facilitate the
reduction of PdII species to Pd0 complexes. Such a re-
duction, a mechanism for which has been proposed by Mc
Crindle,[23] is classical in π-allyl palladium chemistry.[24]
Our goal in this work was to determine conditions for
efficient conversion of the sugar into monooctadienyl
ethers, without seeking either a particular regioselectivity or
a particular linear/branched C-8 chain ratio in the grafting
onto the hydroxy functions. The application of conditions
inspired by Hill[7] in an iPrOH/H2O mixture were disap-
pointing, since the degree of conversion attained only 21%
and a non-negligible amount of octadienol was observed
(Table 1, Entry 1). Since water was a competing reagent, we
decided to switch to an exclusive organic medium; DMF,
With the two best amines, we also studied the influence
which dissolves the sugar and the reaction products, seemed of the amine/Pd ratios, which could be important if the acti-
suitable to us. In this solvent, both pentoses (-xylose or - vation step was to concern the reduction of the metal
arabinose) exhibited similar behaviour: less than 40% of (Table 2). For the degree of conversion of the sugar, the best
Table 1. Preliminary experiments
Entry[a]
Sugar
Solvent
Additive
equiv./Pd
Sugar
Selectivity[c] [%]
monoethers polyethers
By-products [%]
conv.[b] [%]
1
2
3
4
5
1
1
2
1
2
iPrOH/H2O (80:20)
DMF
DMF
DMF
DMF
Ϫ
Ϫ
Ϫ
21
31
39
51
56
95
84
89
90
95
5
16
11
10
5
11[d]
68[e]
85[e]
32[e]
77[e]
NEt3 (20)
NEt3 (20)
[a] Conditions: Pd(acac)2 4.4 ϫ 10Ϫ5 mol; molar ratio: sugar/butadiene/Pd/PPh3 ϭ 150:900:1:3; 1 g of pentose in 25 mL of solvent; 75 °C;
[b]
[c]
[d]
140 min.
Determined by GC. Evaluated by GC, the polyethers being mainly diethers.
By-products consist of butadiene dimers,
[e]
octadienol as the major compound and its isopropyl ether. By-products are mainly butadiene dimers.
Figure 1. Effect of tertiary amines on the arabinose conversion in butadiene telomerization; conditions: Pd(acac)2 4.4 ϫ 10Ϫ5 mol; molar
ratio: -arabinose/Pd/PPh3/butadiene/amine ϭ 150:1:3:900:20; temperature 75 °C; time 140 min, 1 g of -arabinose in 25 mL DMF
Eur. J. Org. Chem. 2004, 2914Ϫ2922
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´
B. Estrine, S. Bouquillon, F. Henin, J. Muzart
FULL PAPER
Table 2. Influence of the amine/Pd ratios on the arabinose transformation in butadiene telomerization
Entry[a]
Amine
Sugar
Selectivity[b] [%]
monoethers polyethers
By-products[c] [%]
molar ratio amine/palladium
conv.[b] [%]
1
2
3
4
5
6
7
8
0
31
51
53
58
46
54
44
22
84
90
91
91
91
94
95
100
16
10
9
9
9
6
5
0
68
32
10
10
Et3N (20)
Et3N (84)
Et3N (150)
Et3N (300)
(iPr)2EtN (20)
(iPr)2EtN (150)
(iPr)2EtN (300)
5
[d]
11
[d]
[a]
Conditions: Pd(acac)2 4.4 ϫ 10Ϫ5 mol; molar ratios: sugar/butadiene/Pd/PPh3 ϭ 150:900:1:3; 75 °C; 140 min, 1 g of -arabinose in 25
[b]
[c]
[d]
mL DMF. GC determination. By-products are mainly butadiene dimers. Not determined.
ratio was about 150 with triethylamine (Entries 2Ϫ5), much amount of phosphane is reported in Table 3. With or with-
lower with diisopropylethylamine (Entries 6Ϫ8). In these out amine, one equiv. of phosphane per palladium led to
experiments, the selectivity towards monoetherification was the best degree of conversion of the sugar (Entries 3, 6, 11,
lower in the absence of amine (Entry 1) and remained con- 12). The use of one or two equivalents of phosphane also
stant for different amounts of the same amine (Entries 2Ϫ4 corresponded with a decrease in the loss of butadiene by
and 6Ϫ8). With triethylamine it seems that an excessive dimer formation, which could be of interest for practical
stoichiometry versus the sugar was detrimental to the de- application (Entries 3, 5, 6, 9Ϫ11). The selectivity towards
gree of conversion (Entry 5). No such amine effect has pre- monoethers was influenced by the relative amount of phos-
viously been described for a telomerization reaction: even if phane: the best selectivity was observed for a P/Pd ratio of
the amine plays a role during the reduction of palladium 3 in the presence of amine (Entries 4, 8) and of 2 in its
salt, it could also stabilise active palladium species by coor- absence (Entry 2). When the amount of phosphane was be-
dination[25,26] or modify the nucleophilic character of the low 1 equiv. per palladium, the drop in the level of conver-
sugar (in establishing hydrogen bonds, for example). When sion might be explained by precipitation of palladium black
the relative amount of triethylamine was increased, we ob- (Entry 7). Such slight precipitation was often observed at
served a parallel decrease in the butadiene dimer by-prod- the end of the reaction for a P/Pd ratio of 1, while a clear
ucts. Possible explanations could involve both sugar acti- yellow solution resulted for P/Pd ϭ 2 or 3. At this stage of
vation or stabilization of a palladium species involved in the the study, we noticed that a decrease in the amount of sol-
telomerization catalytic cycle.
vent may modify the results: both the degree of conversion
We continued our investigations by studying the influence of the sugar and the selectivity are improved for P/Pd ϭ 2
of the nature and amount of phosphane, usually crucial (Entry 10 versus 9), but they remain similar for P/Pd ϭ 1
parameters in telomerization.[2,13,16,22,27,28] The effect of the (Entry 12 versus 11). We had already noticed some concen-
Table 3. Influence of the amount of triphenylphosphane
Entry[a]
Amine
Sugar
Selectivity [%]
monoethers
polyethers[c]
By-products [%][d]
molar ratio amine/palladium
P/Pd
conv. [%][b]
1
2
3
4
5
6
7
8
9
0
0
0
3
2
1
3
2
1
0.5
3
2
31
48
60
54
58
64
38[f]
58
68
81
84
85
84
88
80
94
90
80
95
91
78
86
76
73
16
12
20
6
10
20
5
21
[e]
2
15
2
(iPr)2EtN (20)
(iPr)2EtN (20)
(iPr)2EtN (20)
(iPr)2EtN (20)
Et3N (150)
Et3N (150)
Et3N (150)
Et3N (150)
Et3N (150)
Ͻ1
[e]
9
10
2
2
22
12
24
27
10[g]
11
12[h]
2
1
1
Ͻ1
[e]
[a]
Conditions:. Conditions: Pd(acac)2 4.4 ϫ 10Ϫ5 mol; molar ratios: sugar/butadiene/Pd ϭ 150:900:1; 75 °C; 140 min, 1 g of -arabinose
in 25 mL DMF. [b] GC yields. Diethers are the major products, while yields of triethers remained below 2%. [d] GC yields of butadiene
dimers related to the quantity of butadiene introduced (nonane as internal standard). Not determined. Formation of a palladium
black precipitate. As Entry 9 in using only 5 mL of DMF. As Entry 11 in using only 5 mL of DMF.
[c]
[e]
[f]
[g]
[h]
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Eur. J. Org. Chem. 2004, 2914Ϫ2922

Telomerization of Butadiene with L-Arabinose and D-Xylose in DMF
FULL PAPER
tration effect in the telomerization reaction of butadiene eficial for selectivity towards the monoether, but the degree
with protected carbohydrates and proposed intervention of of conversion of the sugar was slightly reduced (Entry 3).
these telogens as stabilising ligands.[29]
It was interesting to exchange one phenyl group in the PPh3
The above observations prompted us to use more concen- for a methyl, since high levels of conversion and selectivity
trated solutions of sugar (1 g in 5 mL of DMF instead of were observed (Entry 8). Other combinations of aryl-alkyl
25 mL) with a P/Pd ratio of 2, these conditions seeming or trialkylphosphanes were less efficient (Entries 9Ϫ11).
a good compromise with regard to sugar transformation, Among the diphosphanes tested, only dppp afforded good
monoether formation, the stabilisation of the active pal- results (Entries 12Ϫ14), unlike in the telomerization with
ladium species and butadiene dimerisation.
methanol, where the best activity was observed with dppb,
The influence of the nature of the phosphane is reported other bidentate ligands being believed to give inactive met-
in Table 4. Since arabinose and xylose gave analogous re- allacycles.[28] Some dialkylamino-arylphosphane ligands
sults under similar conditions (Entries 2 and 3), the runs in showed good results (Entries 15, 16), decreasing with
this table were carried out indiscriminately with either one monoalkylamino-bis(arylphosphanes) (Entry 17) or triami-
of them. In terms of the degree of conversion of the sugar, nophosphane (Entry 18). In this last case, the presence of
a methyl or methoxy donating group attached to arylphos- phosphorus and nitrogen as chelating atoms might entail
phanes seemed more efficient than a chloro group (Entries too strong coordination to the metal, inhibiting the cata-
3Ϫ5 versus 6). We also tested the more strongly donating lytic activity. Finally, triethylphosphite was not suitable for
tris(trimethoxyphenyl)phosphane, the efficiency of which in this telomerization reaction (Entry 19).
the telomerization of isoprene with amines was related to
According to Tolman,[31] concerning the structures of
its ability to promote the formation of active (L1Pd0) com- phosphanes, some electronic parameters such as the P-do-
plexes,[30] but a drop in the degree of conversion was ob- nor character [correlated to the ν(CO) frequencies of com-
served (Entry 7). The use of o-tolyl phosphane was ben- plexes LNi(CO)3] and steric effects (evaluated as the ligand
Table 4. Effect of the nature of the phosphane on sugar transformation in butadiene telomerization
[a]
Conditions: Pd(acac)2 4.4 ϫ 10Ϫ5 mol; molar ratios sugar/Pd/P/butadiene/Et3N ϭ 150:1:2:900:150; 75 °C; 45 min; 1 g of sugar in 5
[b]
[c]
mL DMF.
Determined by GC. Under these conditions, the loss of butadiene by dimerization was generally low (Ͻ3%). Reaction
time: 30 min. Abbreviations: biph ϭ o-biphenylyl, Cy ϭ cyclohexyl, dppe ϭ diphenylphosphanylethane, dppp ϭ diphenylphosphanylpro-
pane, dppb ϭ diphenylphosphanylbutane.
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´
B. Estrine, S. Bouquillon, F. Henin, J. Muzart
FULL PAPER
cone angle θ), could influence the reaction efficiency. The
steric and electronic maps of the ligands[31,32] we have used
are shown in Figure 2. The best ligands associated with the
best sugar conversions are situated in a narrow horizontal
region corresponding to medium P-donating ligands. The
cone angles of these ligands varied from 136° for PPh2Me
to 194° for tri(oTol) phosphane. Such results indicated that
electronic parameters were prevailing over steric ones with
regard to the degree of conversion of the sugar. Crowding
of the phosphane, however, had an influence on the course
of the reaction: the reaction rate decreased as shown in En-
tries 1 and 4, in which the degree of conversion of the sugar
reached 97% in 35 min with PPh3 and 86% in 45 min with
P(oTol)3. In Table 4, a high selectivity for the monotelomer
is often concomitant with a low degree of conversion. Ac-
cordingly, we might suspect that the low level of conversion
observed with the use of tris(trimethoxyphenyl)phosphane
(Entry 7) is correlated with its strong basic character,[33] and
the good selectivity towards monoethers may be a conse-
quence of the low conversion or due to steric effects.
Figure 2. Steric and electronic map of the phosphanes; the νCO
values stem from IR studies of [Ni(CO)3PR3] complexes by Tol-
man[31] and θ correspond to the cone angles of the phosphane[31,32]
on the nature of the additive. A prolonged reaction time
The observation of a high selectivity towards the mono- significantly increased the degree of conversion of the sugar
substitution product is also an important feature corre- only in the absence of amine (Entries 1, 2 vs. Entries 3, 4
sponding to our objectives. Obviously, for a high degree of or 5, 6) and curiously the transformation of monoethers
conversion of the sugar, the initially formed monoether be- into polyethers was not operative with triethylamine as ad-
came a competitive substrate in telomerization. We have ditive. The black palladium precipitate observed at the end
studied the monoethers’ ability to undergo such a trans- of the longer reaction time (Entries 4, 6) may partially ex-
formation, carrying out reactions for either 140 or 320 min plain the catalyst deactivation.
and with a PPh3/Pd ratio of 1 (Table 5). Under these con-
Solvents other than DMF were also tested (Table 6).
ditions, the behaviour of the monoether seemed to depend THF, CH2Cl2 or toluene, which did not dissolve the sugar
Table 5. Influence of the reaction time on the selectivities of sugar transformation.
Entry[a]
Time (min)
Additive (molar ratio amine/Pd)
Sugar
Selectivity [%][b]
monoethers polyethers
conv. [%][b]
1
2
3
4
5
6
140
320
140
320
140
320
Ϫ
Ϫ
60
72
84
88
64
67
80
69
76
76
80
64
20
31
24
24
20
36
Et3N (150)
Et3N (150)
(iPr)2EtN (20)
(iPr)2EtN (20)
[a] Conditions: Pd(acac)2 4.4 ϫ 10Ϫ5 mol; molar ratios sugar/Pd/PPh3/butadiene ϭ 150:1:1:900/; 75 °C; 1 g of -arabinose in 25 mL DMF.
[b]
Determined by GC.
Table 6. Solvent effect in butadiene telomerization with arabinose
Entry[a]
Solvent (g sugar/mL)
Time (min)
Sugar
Selectivity [%][b]
diethers
Butadiene
conv. [%][b]
monoethers
triethers
dimers [%][c]
1
2
3
4
5
6
7
DMF (1/25)
140
140
140
180
120
45
68
0
96
29
100
85
33
78
0
48
83
21
79
100
22
0
49
17
57
15
0
0
0
3
0
22
5
2
[d]
THF (0.5/25)
CH3CN (0.5/20)
CH2Cl2 (0.5/20)
tBuOH (1/15)
DMSO (1/5)
3
[d]
[d]
5
17
Toluene (0.5/20)
180
0
[a]
Conditions: Pd(acac)2 4.4 ϫ 10Ϫ5 mol; molar ratios -arabinose/Pd/PPh3/butadiene/NEt3 ϭ 150:1:2:900:150 (Entries 1, 5, 6) and
[b]
[d]
[c]
75:1:2:900:150 (Entries 2, 3, 4, 7); 80 °C except Entry 1: 75 °C.
quantity of butadiene introduced (nonane as internal standard). Not determined.
Determined by GC. GC yields of butadiene dimers related to the
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Telomerization of Butadiene with L-Arabinose and D-Xylose in DMF
FULL PAPER
Table 7. Effect of the nature of the palladium precursor in the telomerization of butadiene with -arabinose
Entry[a]
"Pd"
Sugar
Selectivity [%]
diethers
conv. [%][b]
monoethers (yield[c])
triethers
1
2
3
Pd(acac)2
Pd(OAc)2
PdCl2
PdCl2(PhCN)2 or PdCl2(MeCN)2
Pd2(dba)3·CHCl3
81
94
8
10
79
86 (69)
73 (68)
100 (8)
100 (10)
90 (71)
12
24
0
0
9
2
3
0
0
1
4
5[d]
[a]
Conditions: Pd 4.4 ϫ 10Ϫ5 mol; molar ratios -arabinose/Pd/PPh3/butadiene/NEt3 ϭ 150:1:2:900:150; 75 °C; 45 min; 1 g of pentose in
[b]
[c]
[d]
5 mL DMF. GC yields. total yield of monoethers (conv. ϫ selectivity). PPh3/Pd ϭ 1.
at room temperature, afforded poor levels of conversion
(Entries 2, 4 and 7). The enhanced reactivity evident in
acetonitrile (Entry 3) and tert-butyl alcohol (Entry 5) was
detrimental to the monoether selectivity. DMSO (Entry 6)
would be the best solvent in terms of the GC results. How-
ever, the difficulties in removing this solvent from the prod-
ucts made us prefer DMF.
Other catalytic precursors were examined (Table 7). Ex-
cept with palladium complexes containing chloride ions
(Entries 3, 4), we observed comparable results for the total
yields of monoethers (Entries 1, 2, 5). The low reactivity
when PdCl2 is employed could not be attributed to its poor
solubility in the reaction medium (Entry 3), since the use
of the more soluble PdCl2(RCN)2 [R ϭ Ph or Me] did not
provide any improvement (Entry 4). Such an inhibition of
palladium reactivity by chloride ions is not a general feature
of the telomerization reaction,[30] but has previously been
noticed and explained in terms of the strong coordinating
properties of halogen in relation to other ligands.[34] With
other precursors, the variations concern the conversion and
the selectivity values. Pd(acac)2 remained the best catalyst
source, if the possible reuse of the unchanged sugar is taken
into account (Entry 1). Indeed, Pd(OAc)2 gave the best de-
gree of conversion of the sugar, but with a lower selectivity
Figure 3. Structures of the major compounds resulting from the
telomerization after their acetylation
ever, in non-negligible amounts (l/b around 80:20 from -
xylose). During the first chain grafting, etherification oc-
curred mainly at the anomeric hydroxy group, which is
probably due to its higher acidity. Indeed, the anomeric
hydroxy group (pKa ഠ 12) is more acidic than simple al-
cohols (pKa ഠ 16), due to inductive electron withdrawal by
the endocyclic oxygen.[37] As a consequence, the anomeric
hydroxy proton is more active during the key step of pro-
tonation of the (η1,η3-octadienyl)palladium intermedi-
ate,[12,13] inducing the observed selectivities. The xylose de-
rivatives adopted the pyranose forms while the furanose
forms were also present in the arabinose derivatives. As we
have previously discussed,[29] the ratios of the glycoside tau-
tomers are different from those in the starting materials.
.
(Entry 2). With Pd2(dba)3 CHCl3 as catalyst (Entry 5), the
results were similar to those seen with Pd(acac)2. Thus, it
appeared to be no advantage in starting from Pd0 rather
than PdII as the palladium source, as already mentioned for
butadiene telomerization with methanol.[35]
The structures of the major resulting materials (Figure 3)
were established by their transformation into peracetylated
derivatives, followed by purification. The obtained products
were compared with the peracetylated starting sugars[36]
and the compounds resulting from the telomerization of
butadiene with 2,3,4-tri-O-acetylated pentopyranoses.[29]
The major ethers consist of approximately 50% of 3α and
26% of 3β from -xylose and 39% of 4α, 22% of 4β, 4% of
5α and 4% of 5β from -arabinose. The other products in-
cluded isomers of the above compounds with branched
Conclusion
By careful modification of the experimental conditions,
chains instead of linear ones and isomeric forms of di- and we have succeeded in the selective glycosidation of free pen-
tri-octadienylethers, no C-4 or C-16 adducts being detected toses by a Pd-catalysed telomerization of butadiene in
by GC/MS. During this work we did not determine the lin- DMF. The catalytic system has been optimised by adjust-
ear/branched ratio exactly, in view of the complicated mix- ment of quantities of amines and phosphanes, the latter
tures obtained, the branched compounds being found, how- having medium donating properties. The process, which re-
Eur. J. Org. Chem. 2004, 2914Ϫ2922
www.eurjoc.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2919

´
B. Estrine, S. Bouquillon, F. Henin, J. Muzart
FULL PAPER
General Procedure for the Telomerization of Butadiene with Pen-
toses: Pd(acac)2 and the ligand were charged into a sealed 50-mL
stainless-steel autoclave (Parr Instrument Company). The autoclave
was evacuated and filled with argon three times. A degassed DMF
solution of the pentose was transferred under argon from a Schlenk
tube into the autoclave. Gaseous 1,3-butadiene was condensed at
Ϫ20 °C in a Schlenk tube and then transferred into the cooled
autoclave. After closure, the autoclave was placed in an oil bath at
75 °C. Stirring was started for the time indicated in Tables 1Ϫ7.
After cooling, remaining butadiene, volatile dimers and solvent
were condensed in a Schlenk tube. Nonane was then added as in-
ternal standard in order to quantify the butadiene dimers by GC
(isotherm 50 °C; 15 min, and then: 50Ϫ150 °C, 10 °C/min).
The residual mixture containing unreacted pentoses and octadienyl
ethers of pentoses was acetylated with an excess of acetic anhy-
dride/pyridine over 12 h. After extraction with ether the mixture
was analysed by GC/MS, with 9-decen-1-ol as standard. The
groups of compounds were separated by successive chromatogra-
phy.
quires neither activation nor protection of the sugar and
the glycosyl acceptor, provides surfactant molecules with
non-ionic and biodegradable heads.[38]
Experimental Section
General: 1H and 13C NMR were recorded on a Bruker AC 500
spectrometer (1H, 500 MHz; 13C, 125.7 MHz) and referenced to
TMS. Elemental analyses were carried out on a PerkinϪElmer
CHN 2400 instrument. GC analyses were recorded on
a
HewlettϪPackard HP-6890 gas chromatograph, fitted with a DB-
1 capillary column (25 m, 0.32 mm), a flame ionisation detector
and a HP-3395 integrator. GC/MS spectra (EI or CI-NH3) were
performed on a Finnigan Trace GC 2000 Series Thermoquest spec-
trometer, fitted with a DB-1 capillary column (25 m, 0.32 mm) and
under the following conditions (for the sugar derivatives): helium
as vector gas (0.5 bar), injector: 250 °C, column: 150Ϫ300 °C (5
°C/min). Chromatography was carried out on SDS Silica 60
(40Ϫ63 µm), Art 2050044 (flash chromatography, petroleum ether/-
ethyl acetate, 1:1 for -arabinose derivatives and 7:3 for -xylose
derivatives), silica 60 F254 (TLC plates) or semi-preparative HPLC,
LC-10AS Shimadzu, UV detection (210 nm), column Si-60 LiCh-
rospher, 10 µm (elution with hexane/2-propanol, 97:3, 3.5 mL/min
for -arabinose derivatives and 99:1, 5 mL/min for -xylose deriva-
tives).
Three fractions were then collected:
The least polar fraction (Rf Ͼ 0.8, petroleum ether/ethyl acetate,
7:3) was a mixture of peracetylated polyoctadienyl ethers of pen-
toses and butadiene oligomers. GC/MS-CI (NH3) confirmed the
presence of peracetylated di- and trioctadienyl ethers of pentoses.
Peracetylated trioctadienyl ethers of -arabinose: Tr ϭ 30.49, 30.73,
31.04, 31.36, 31.41, 31.70, 31.02. MS/CI (NH3): m/z (%) ϭ 534
(100) [M ϩ 18], 391 (25) [M Ϫ OC8H13].
Peracetylated dioctadienyl ethers of -arabinose: Tr ϭ 25.97, 25.07,
25.37, 25.34, 25.69, 25.77 min. MS/CI (NH3): m/z (%) ϭ 468 (57)
[M ϩ 18], 325 (100) [M Ϫ OC8H13].
The fraction corresponding to a Rf of 0.6 (petroleum ether/ethyl
acetate, 7:3) was a mixture of peracetylated monooctadienyl ethers
as analysed by GC/MS-CI (NH3).
Tr ϭ 15.48, 15.95, 17.74, 17.98 min. MS/CI (NH3): m/z (%) ϭ 402.2
(100) [M ϩ 18].
The solvents, the substrates -arabinose and -xylose and the PdII
catalysts were commercially available (Aldrich, Acros or Strem
.
Chemicals) and were used as received. Pd2(dba)3 CHCl3 was pre-
pared by a literature method.[39] Butadiene N25 from Air Liquide
was used without further purification. The amines employed were
distilled from KOH before use. Commercial phosphanes from
Strem Chemicals were used as supplied and aminodiphenylphos-
phanes prepared according to the literature,[40,41] morpholinodi-
phenylphosphane[40] and N,N-diethylaminophosphane[41] having
been described.
The most polar fraction contained the peracetylated residual pen-
tose in four forms (pyranosic, furanosic and anomeric isomers).
Tr ϭ 9.44, 9.64, 9.90, 10.04 min. MS/CI (NH3): m/z (%) ϭ 336
(100) [M ϩ 18], 259 [M Ϫ OAc].
The following glycosides exhibit spectroscopic data analogous to
those previously described:[29] 2Ј-(E)-7Ј-octadienyl 2,3,4-tri-O-ace-
tyl-β--xylopyranoside (3β), 2Ј-(E)-7Ј-octadienyl 2,3,4-tri-O-acetyl-
α--xylopyranoside (3α), 2Ј-(E)-7Ј-octadienyl 2,3,4-tri-O-acetyl-α-
-arabinopyranoside (4α), 2Ј-(E)-7Ј-octadienyl 2,3,4-tri-O-acetyl-β-
-arabinopyranoside (4β). Two monooctadienyl ethers, 2Ј-(E)-7Ј-
octadienyl 2,3,4-tri-O-acetyl-β--arabinofuranoside (5β) and 2Ј-
(E)-7Ј-octadienyl 2,3,4-tri-O-acetyl-α--arabinofuranoside (5α),
were also isolated and characterized.
A solution of Ph2PCl (10 mmol, 1.8 mL) in diethyl ether (10 mL)
was added over 2 h, at Ϫ20 °C under argon, to a solution of decyla-
mine (5 mmol, 1 mL) in Et3N (5 mL). After further stirring at room
temperature for 4 h, the suspension was filtered through Celite to
remove the triethylammonium salt. Diethyl ether was evaporated
under reduced pressure to afford the labile N,N-bis(diphenylamino-
2Ј-(E)-7Ј-Octadienyl 2,3,5-Tri-O-acetyl-β-l-arabinofuranoside (5β):
1
IR: ν˜ ϭ 2926, 2843, 1742, 1441, 1375, 1223, 700 cmϪ1. H NMR
(500 MHz, CDCl3): δ ϭ 1.45 (quint, 2 H, J5Ј,4Јϭ J5Ј,6Јϭ 7.3 Hz, 5Ј-
H), 2.00Ϫ2.10 (m, 13 H, ϪCOCH3, 4Ј-H, 6Ј-H), 3.95 (dd, 1 H,
phosphanyl)decylamine as a yellow oil: 1.05 g, 40%. IR: ν˜ ϭ 2923, J1Јb,1Јa ϭ 12.2, J1Јb,2Ј ϭ 6.8 Hz, 1Јb-H), 4.07 (ddd, 1 H, J4,3 ϭ 6.7,
2853, 1961, 1893, 1819, 1774, 1590Ϫ1436, 1206, 1122, 743 cmϪ1
.
J4,5a ϭ 4.1, J4,5b ϭ 5 Hz, 4-H), 4.12Ϫ4.22 (m, 2 H, 5b-H, 1Јa-H),
4.45 (dd, 1 H, J5a,4ϭ 4.1, J5a,5bϭ 11.5 Hz, 5a-H), 4.95Ϫ5.05 (m, 3
H, 2-H, 8Јa-H, 8Јb-H), 5.12 (d, 1 H, J1,2 ϭ 4.6 Hz, 1-H), 5.38 (dd,
1H NMR (250 MHz, CDCl3): δ ϭ 0.75Ϫ1.25 (m, 19 H, 5Ϫ13 H),
3.15 (m, 2 H, 4-H), 7.15 Ϫ7.35 (m, 20 H, 1-H, 1Ј-H, 2-H, 2Ј-H, 3-
H) ppm. 13C NMR (250 MHz, CDCl3): δ ϭ 14.0 (C-13), 22.6Ϫ29.3 1 H, J3,2 ϭ 6.7, J3,4 ϭ 6.7 Hz, 3-H), 5.44 (ddd, 1 H, J2Ј,1Јa ϭ 7.1,
(m, C6Ϫ10, C-12), 31.2 (C-11), 31.8 (C-5), 53.0 (t, JCϪN ϭ 11 Hz,
J2Ј,1Јb ϭ 6.8, J2Ј,3Ј ϭ 15.5 Hz, 2-H), 5.70 (dt, 1 H, J3Ј,2Ј ϭ 15.5,
C-4), 127.9Ϫ139.6 (m, Carom) ppm. 31P NMR (250 MHz, CDCl3): J3Ј,4Ј ϭ 6.7 Hz, 3Ј-H), 5.80 (ddt, 1 H, J7Ј,6Јa ϭ 6.8, J7Ј,8Јa ϭ 10,
.
δ ϭ 62.6 ppm. C34H41NP2 HCl (561.5): calcd. C 72.65, H 7.53, N J7Ј,8Јb ϭ 18 Hz, 7Ј-H) ppm. 13C NMR (500 MHz, CDCl3): δ ϭ
2.49; found C 71.41, H 7.70, N 2.42 (the compound is easily oxid-
ized, explaining the deviation of the elemental analysis). GC/MS
(EI): m/z ϭ 526 [M ϩ1] (100).
20.5, 20.6, 20.7 (3 CH3), 28.1 (C-5Ј), 31.5, 33.1 (C-4Ј, C-6Ј), 65.3
(C-5), 68.3 (C-1Ј), 75.8 (C-3), 76.7 (C-2), 78.6 (C-4), 99.0 (C-1),
114.6 (C-8Ј), 125.2 (C-2Ј), 135.2 (C-3Ј), 138.5 (C-7Ј) 170.2, 170.3,
2920
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Eur. J. Org. Chem. 2004, 2914Ϫ2922

Telomerization of Butadiene with L-Arabinose and D-Xylose in DMF
FULL PAPER
[12b]
R. Benn, P. W. Jolly, R. Mynott, B. Raspel, G. Schenker,
170.6 (3 CO) ppm. C19H28O8 (384.4): calcd. C 59.36, H 7.34; found
C 59.52, H 7.63. GC/MS (NH4ϩ): m/z ϭ 402 [M ϩ 18] (100), 259
[M Ϫ 125], 78%.
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2Ј-(E)-7Ј-Octadienyl 2,3,5-Tri-O-acetyl-α-l-arabinofuranoside (5α):
1
IR: ν˜ ϭ 2926, 2843, 1742, 1441, 1375, 1223, 700 cmϪ1. H NMR
(500 MHz, CDCl3): δ ϭ 1.45 (quint, 2 H, J5Ј,4Ј ϭ J5Ј,6Ј ϭ 7.5 Hz,
5Ј-H), 2.00Ϫ2.15 (m, 13 H, ϪCOCH3, 4Ј-H, 6Ј-H), 4.10Ϫ4.20 (m,
3 H, 3-H, 5b-H, 1Јb-H), 4.30 (m, 3 H, 4-H, 5a-H, 1Јa-H),
4.95Ϫ5.05 (m, 3 H, 2-H, 8Јa-H, 8Јb-H), 5.15 (d, 1 H, J1,2 ϭ 2.5 Hz,
1-H), 5.50 (ddd, 1 H, J2Ј,1Јa ϭ 6.8, J2Ј,1Јb ϭ 5.6, J2Ј,3Јϭ 12.3 Hz, 2Ј-
H), 5.70 (dt, 1 H, J3Ј,2Ј ϭ 12.3, J3Ј,4Ј ϭ 6.7 Hz, 3Ј-H), 5.80 (ddt, 1
H, J7Ј,6Ј ϭ 6.6, J7Ј,8Јa ϭ 6.7, J7Ј,8Јb ϭ 17.1 Hz, 7Ј-H) ppm. 13C NMR
(500 MHz, CDCl3): δ ϭ 20.5, 20.6, 20.7 (3 CH3), 28.1 (C-5Ј), 31.6,
33.1 (C-4Ј, C-6Ј), 63.6 (C-5), 68.7 (C-1Ј), 76.8 (C-3), 79.5 (C-2),
83.0 (C-4), 107.4 (C-1), 114.6 (C-8Ј), 125.3 (C-2Ј), 134.6 (C-3Ј),
138.4 (C-7Ј) 170.2, 170.3, 170.6 (3 CO) ppm. C19H28O8 (384.4):
calcd C 59.36, H 7.34; found C 59.52, H 7.63. GC/MS (NH4ϩ):
m/z ϭ 402 [M ϩ 18] (100), 259 [M Ϫ 125], 78%.
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