Ruthenium-catalyzed synthesis of allylic alcohols: Boronic acid as a hydroxide source

Article abstract of DOI:10.1002/chem.200702030

Secondary allylic alcohols were synthesized from linear allylic halides or carbonates using a catalytic amount of a ruthenium complex in the presence of boronic acid. The effects of solvent, base, ruthenium precursor, and boronic acid were fully explored, and the scope of the reaction was extended to various sub-strates. We also describe a preliminary investigation towards an enantioselective process.

Full text of DOI:10.1002/chem.200702030

DOI: 10.1002/chem.200702030
Ruthenium-Catalyzed Synthesis of Allylic Alcohols: Boronic Acid as a
Hydroxide Source
Asmae Bouziane,[a] Marion HØlou,[b] Bertrand Carboni,[a] FranÅois Carreaux,*[a]
Bernard Demerseman,[b] Christian Bruneau,[b] and Jean-Luc Renaud*[c]
Abstract: Secondary allylic alcohols were synthesized from linear allylic halides or
carbonates using a catalytic amount of a ruthenium complex in the presence of
boronic acid. The effects of solvent, base, ruthenium precursor, and boronic acid
were fully explored, and the scope of the reaction was extended to various sub-
strates. We also describe a preliminary investigation towards an enantioselective
process.
Keywords: allylic compounds
allylic substitution asymmetric
synthesis boron catalysis
regioselectivity · ruthenium
·
·
·
·
·
Introduction
metrically substituted substrates has not been widely studied
and still constitutes a challenging research area in asymmet-
ric catalysis. For this type of nucleophilic substitution, pen-
tamethylcyclopentadienylruthenium catalysts have shown
promising properties with respect to regioselectivity in favor
Nucleophilic allylic substitution catalyzed by transition
metals is a powerful tool in organic synthesis and gives
rapid access to functionalized building blocks.[1] The palladi-
um-catalyzed reaction, known as the Tsuji–Trost reaction
with symmetrical allylic substrates,[1] is one of the most pop-
ular model reaction and is often used to evaluate the effi-
ciency of chiral ligands. Moreover, many complexes based
on molybdenum,[2] rhodium,[3] tungsten,[4] palladium,[5] iridi-
um,[6] iron,[7] and ruthenium[8] have demonstrated high po-
tential in the reaction of unsymmetrical allylic derivatives
with carbonucleophiles. However, the nucleophilic allylic
substitution with heteronucleophiles starting from non-sym-
of the branched isomer.[8] Thus, the [Cp*Ru
(MeCN)3]PF6
A
(Cp*=pentamethylcyclopentadienyl, Me=methyl) complex
was recently shown to be appropriate for the synthesis of
aryl allyl ethers starting from allylic halides and phenols,[9]
and the [Cp*Ru
N
N
cursors have revealed catalytic activity allowing the direct
involvement of neutral undeprotonated soft carbon pronu-
cleophiles, aliphatic alcohols, or amines.[10]
To expand the scope of nucleophiles in catalytic processes
involving ruthenium complexes, we attempted the reaction
of cinnamyl carbonate with phenylboronic acid. The expect-
ed product, which results from the transfer of a phenyl
group through a classical transmetalation from boron to a
transition metal,[11,12] was not formed, and only the branched
and linear allylic alcohols were isolated as shown in
Scheme 1. To the best of our knowledge, this reaction which
corresponds to the delivery of an hydroxy group via a boron
intermediate was unprecedented in the literature.[13] Taking
[a] A. Bouziane, Dr. B. Carboni, Dr. F. Carreaux
Sciences Chimiques de Rennes
IngØniØrie chimique et molØcules pour le vivant
UMR 6226: CNRS-UniversitØ de Rennes 1
Campus de Beaulieu-35042 Rennes Cedex (France)
Fax : (+33)223-236-939
E-mail: francois.carreaux@univ-rennes1.fr
[b] M. HØlou, Dr. B. Demerseman, Dr. C. Bruneau
Sciences Chimiques de Rennes, Catalyse et OrganomØtalliques
UMR 6226: CNRS-UniversitØ de Rennes 1
Campus de Beaulieu-35042 Rennes Cedex (France)
[c] Dr. J.-L. Renaud
Sciences Chimiques de Rennes, Chimie Organique et SupramolØcu-
laire
UMR 6226: Ecole Nationale SupØrieure de Chimie de Rennes
Campus de Beaulieu-35700 Rennes (France)
Fax : (+33)223-238-102
E-mail: jean-luc.renaud@univ-rennes1.fr
jean-luc.renaud.1@ensc-rennes.fr
Scheme 1. Allylic alcohol synthesis.
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Chem. Eur. J. 2008, 14, 5630 – 5637

FULL PAPER
Table 1. The influence of the catalyst, solvent and boronic acid on the re-
activity and the regioselectivity.[a]
into account that allylic alcohols are important intermedi-
ates in the synthesis of biologically active compounds[14] and
that phenyl boronic acid is commercially available, cheap
and non toxic, we explored the scope and limitation of this
new process for the synthesis of allylic alcohols. Other cata-
lytic methods for the preparation of allylic alcohols are
based on the use of benzylic alcohol,[15,16] hydroxylamines,[17]
or silanols as nucleophiles in allylic substitution.[18] However,
all of them require a subsequent deprotection step, and the
chemoselectivity of such reactions often lead to undesired
by-products.[19] Although some examples of palladium-cata-
lyzed deracemization of allylic carbonates with water have
been reported,[20] the need for new nucleophiles providing a
more straightforward synthesis of allylic alcohols has already
been emphasized. We report herein a new and unprecedent-
ed introduction of hydroxy groups starting from linear allylic
carbonates or halides by ruthenium-catalyzed allylic substi-
tution using boronic acid as the source of hydroxide and our
preliminary efforts toward an enantioselective procedure.
Entry
X
Ar
Catalyst[b] Solvent Yield B/L
[%][c] ratio[d]
1
2
3
4
5
6
7
8
9
Cl
OCO2Et
Cl
OCO2Et
OCO2Et
OCO2Et
OCO2Et
Cl
Ph
Ph
–
Ph
Ph
Ph
Ph
Ph
Ph
–
–
2
1
1
1
2
2
CH3CN
CH3CN
CH3CN
THF
CH3CN 90
CH2Cl2 85
CH3CN
CH3CN 80
THF 0
0
0
0
–
–
–
28
60/40
72/28
15/85
/
89/11
/
0
Cl
2
10
11
12
13
14
15
Cl
Cl
Cl
Cl
Ph
2
2
2
2
CH2Cl2 40
CH3CN 74
CH3CN 42
CH3CN 96
CH3CN 34
69/31
67/33
91/9
49/51
18/82
77/23
p-MeOC6H4
o-MeOC6H4
p-NCC6H4
Ph
OCO2Et
Cl
[Ir][e]
[Ir][e]
Ph
THF
47
[a] Conditions: 0.5 mmol of cinnamyl derivative, 0.6 mmol of phenylbor-
onic acid, 0.015 mmol of catalyst, 1.3 mmol of KF in solvent (1 mL) at
Results and Discussion
room temperature. [b] 1: [Cp*Ru(4,4’-tBu2bipy)
(MeCN)3]PF6. [c] Yield of isolated product. [d] B/L ratio=branched/
linear ratio. As determined by 1H NMR spectroscopy with less than 5%
(MeCN)]PF6, 2: [Cp*Ru-
Optimization of the reaction: In a preliminary reaction, one
equivalent of cinnamyl carbonate was treated with 1.2 equiv-
alents of phenylboronic acid in the presence of a catalytic
AHCTREUNG
uncertainty. [e] [{Ir
five days.
A
E
amount of [Cp*Ru(4,4’-di-tert-butylbipyridine)(MeCN)]PF6
G
(1) and an excess of potassium fluoride in THF at room
temperature. The allylic alcohol was isolated in a low yield
(28%) and moderate regioselectivity (60/40 in favor of the
branched isomer, Scheme 1).
tion of cinnamyl carbonate with different nucleophiles
(amine, alcohol, or non-deprotonated carbonucleophiles).[10]
However, in the presence of cinnamyl chloride instead of
cinnamyl carbonate, this catalyst led to the desired com-
pound in good yield and high regioselectivity in acetonitrile
(entry 8, Table 1). In THF or CH2Cl2, either no reaction oc-
curred or lower selectivity was obtained (entries 9,10,
Table 1).
The role of boronic acid was also examined in the optimi-
zation process. An increase of the steric hindrance led to a
slight improvement of the regioselectivity (from 89/11 to 91/
9 in favor of the branched isomer, entries 8 and 12, Table 1)
but had a detrimental effect on the yield (from 80 to 42%).
The presence of an electron-withdrawing group on the aro-
matic substituent of the boronic acid led to an increase in
the reaction rate and an improvement in the yield, but this
enhancement was accompanied by a lack of regioselectivity
(entry 13, Table 1). On the other hand, no reaction was ob-
served with boric acid, which also showed solubility prob-
lems.
It is worth mentioning that without a ruthenium catalyst,
no reaction occurred (entries 1 and 2, Table 1) when cin-
namyl chloride or carbonate and phenylboronic acid were
used. Similarly, without phenylboronic acid, no allylic alco-
hol was obtained (entry 3, Table 1). Having demonstrated
that both the ruthenium catalyst and phenylboronic acid
were essential for this new reaction, we optimized the condi-
tions to improve the regioselectivity. Solvent screening (en-
tries 4–6, Table 1) revealed that acetonitrile provided the
best regioselectivity and yield starting from cinnamyl car-
bonate; the allylic alcohol was isolated in 90% yield in a 72/
28 ratio in favor of the branched isomer. With the [Cp*Ru-
A
(entry 7, Table 1), no reaction was observed. Such behavior
of catalyst 2 was previously observed in the allylic substitu-
Abstract in French: Les alcools allyliques secondaires ont ØtØ
prØparØs à partir de chlorures ou de carbonates allyliques li-
nØaires en prØsence d’acide boronique et d’une quantitØ cata-
lytique de complexe de ruthØnium. Les effets de la base, du
solvant et du prØcurseur de ruthØnium ont ØtØ ØtudiØs. Cette
nouvelle rØaction a ØtØ Øtendue à diffØrents chlorures de cin-
namyle. Lors de cette Øtude, nous dØcrivons d’autre part les
premiers rØsultats en catalyse ØnantiosØlective.
Due to the high efficiency of iridium catalysts in allylic
substitution,[17c] we also tested [IrCl
N
N
cyclooctadiene, Ph=phenyl) in this reaction. However,
whatever the allylic derivative used, higher temperatures
and long reaction times were required, and the yield and the
regioselectivity were also lower (entries 14 and 15, Table 1).
At this stage, this study revealed that the best regioselec-
tivity and yield were obtained in acetonitrile with [Cp*Ru-
Chem. Eur. J. 2008, 14, 5630 – 5637
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J.-L. Renaud, F. Carreaux et al.
Table 3. The preparation of allylic alcohols.[a]
A
droxide donor and cinnamyl chloride as precursor (entry 8,
Table 1).
As the nature of the boron activator is of great impor-
tance in the Suzuki reaction and in the coupling reaction of
allylic derivatives using boron reagents in the presence of
palladium catalyst,[13] the screening of several activators was
carried out (Table 2). Without any activator, no reaction oc-
Entry
Ar
Yield [%][b]
B/L ratio[c]
1
2
3
4
5
6
7
8
9
m-NO2-C6H4
p-NO2-C6H4
o-NO2-C6H4
p-Cl-C6H4
p-Br-C6H4
2,4,6-(Me)3-C6H2
1-Napht
60
75
90
50
66
55
70
90
77
30/70
40/60
65/35
44/56
67/33
70/30
85/15
100/0
98/2
Table 2. The influence of the base on the reactivity and the regioselecti-
vity.[a]
2-Napht
Ph
[a] Conditions : 0.5 mmol of cinnamyl chloride, 0.6 mmol of phenylboron-
ic acid, 0.015 mmol of [Cp*Ru(MeCN)3]PF6, 1.3 mmol of potassium car-
bonate in acetonitrile (1 mL). [b] Yield of isolated product. [c] B/L
ratio=branched/linear ratio. As determined by 1H NMR spectroscopy
with less than 5% uncertainty.
AHCTREUNG
Entry
Base
Yield [%][b]
B/L ratio[c]
1
2
3
4
5
6
–
KF
0
80
40
19
77
55
–
89/11
90/10
67/33
98/2
82/18
K2CO3 (2m)
K2CO3 (0.5m)
K2CO3
(entries 1–5, Table 3). By contrast, with electron-donating
groups on the aromatic ring, the regioselectivity favored the
branched allylic alcohol (entries 6–9, Table 3).
Cs2CO3
[a] Conditions: 0.5 mmol of cinnamyl chloride, 0.6 mmol of phenylboron-
ic acid, 0.015 mmol of [Cp*Ru(MeCN)3]PF6, 1.3 mmol of base in acetoni-
trile (1 mL). [b] Yield of isolated product. [c] B/L ratio=branched/linear
ratio. As determined by 1H NMR spectroscopy with less than 5% uncer-
tainty.
AHCTREUNG
It is worth mentioning that very electron-rich aromatic
derivatives (R=4-Me2N-; 2,4,6-(MeO)3-; 4-MeO-; 4-
(C6H5CH2O)-) led exclusively to propiophenones in good
yields (69–89% overall yields from the allylic chloride,
Scheme 2 and Table 4). We have shown that their formation
resulted from the initial generation of branched allylic alco-
hols followed by subsequent isomerization to ketones
(Scheme 2, Table 4).[23]
curred (entry 1, Table 2). The best result was obtained with
potassium carbonate as shown in Table 2. When solid potas-
sium carbonate was used, the regioselectivity increased to
98/2 in favor of the branched isomer (entry 5, Table 2). With
cesium carbonate or an aqueous solution of potassium car-
bonate, yields and regioselectivities were much lower.[21] It is
worth mentioning that water had a detrimental effect on
both the reactivity and the regioselectivity in this new cata-
lytic process (entries 3–5, Table 2).
Starting from the idea that the formation of a borate spe-
cies was a necessary condition for the transfer of a hydroxy
Scope of the reaction: To evaluate the scope of this new cat-
alytic reaction, we prepared several aromatic allylic halides
in three steps from commercially available aldehydes ac-
cording to known procedures. The Horner–Wadworth–
Emmons reaction was carried out following a known proce-
dure at room temperature in acetonitrile with DBU/LiCl
(DBU=1,8-diazabicyclo
[5.4.0]undec-7-ene) as base.[22] The
A
Scheme 2. Cascade allylic substitution/isomerization reaction catalyzed
by ruthenium complexes.
unsaturated esters were isolated after purification in high
yields (83–100%). After reduction to allylic alcohols with
DIBAL-H (DIBAL-H=diisobutylaluminum hydride) in tol-
uene at À788C (87–98% yield), chlorination in the presence
of thionyl chloride led to the corresponding allylic chlorides
in good yields (76–90%).
Starting from these allylic derivatives, under our reaction
conditions, we were able to isolate the allylic alcohols in
moderate to good yields (Table 3). With aromatic allylic
compounds bearing electron-withdrawing groups, the regio-
selectivity mainly favored the linear alcohol, except with
NO2 and Br in the ortho and para positions, respectively
Table 4. The preparation of propiophenone derivatives using a cascade
allylic hydroxylation/isomerization.[a]
Entry
R
Yield [%][b]
1
2
3
4
2,4,6-(OMe)3
p-OMe
p-NMe2
75
89
69
87
p-C6H5CH2O
[a] Conditions: 0.5 mmol of aryl chloride, 0.6 mmol of phenylboronic
acid, 0.015 mmol of [Cp*Ru(MeCN)3]PF6, 1.3 mmol of potassium carbon-
ate in acetonitrile (1 mL). [b] Yield of isolated product.
AHCTREUNG
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Chem. Eur. J. 2008, 14, 5630 – 5637

Allylic Alcohols
FULL PAPER
Table 5. The asymmetric synthesis of cinnamyl alcohol.[a]
group, the catalytic process was performed with an isolated
borate salt. Sodium phenylboronate was prepared by treat-
ment of phenylboronic acid with sodium hydroxide.[24] Start-
ing from this boronate and cinnamyl chloride, the reaction
led to the formation of the allylic alcohol in good yield
(70%) with complete regioselectivity favoring the branched
isomer (Scheme 3). This result indicates that the reaction
can be carried out directly from a borate reagent without
addition of a base/nucleophile and, thus, might be extended
to substrates with base-sensitive functional groups.
Nitrogen
ligands
Yield [%][b]
B/L ratio[c]
ee [%][d]
3
4
5
6
7
8
9
10
60
82
69
82
96
90
98
64
60/40
66/34
61/39
58/42
34/66
42/58
47/53
72/28
9 (S)
5 (S)
11 (S)
17 (S)
7 (R)
2 (S)
0
Scheme 3. Allylic substitution with sodium phenylborate.
Towards an enantioselective process: We have recently dis-
closed the first example of enantioselective allylation involv-
ing a non-symmetrical allylic moiety with ruthenium cata-
41 (R)
lysts; we showed that [Cp*Ru(MeCN)3]PF6 with an optically
A
[a] Conditions: 0.5 mmol of aryl chloride, 0.6 mmol of phenylboronic
acid, 0.015 mmol of [Cp*Ru(MeCN)3]PF6, 0.015 mmol of chiral ligand,
AHCTREUNG
pure bisoxazoline led to very good enantioselectivities
during the allylation of phenol by cinnamyl chloride.[25a]
More recently, complexes containing pyridine-imines[25b,c] or
planar chiral cyclopentadienyl[25d,e] as ligands revealed excel-
lent enantioselectivities in ruthenium-catalyzed Carroll rear-
rangement[25b,c] and allylic substitution reactions.[25d,e] On the
basis of these results, we have selected different ligands in
this new catalytic reaction. In all cases, the alcohols were
isolated in good yields, and the formation of the branched
isomer was always favored except in the presence of ligands
7, 8, and 9 (Table 5). Finally, the additional presence of a
phenyl group at the C(5)-position in 10 (as compared to 3,
Table 5) resulted in a markedly enhanced enantioselectivity
and regioselectivity. The branched allylic alcohol was ob-
tained in 41% ee, with the R isomer as the major isomer.
In light of the different results obtained during this study,
we assume that either potassium carbonate or a fluoride
anion reacts with phenylboronic acid to form in situ an
“ate” complex as depicted in Scheme 4.[26] This intermediate
could undergo a transmetalation in the presence of a ruthe-
1.3 mmol of potassium carbonate in acetonitrile (1 mL) at room tempera-
ture. [b] Yield of isolated product. [c] B/L ratio=branched/linear ratio.
As determined by 1H NMR spectroscopy, the stereochemistry was deter-
mined by comparison with the literature.[18] [d] As determined by HPLC
analysis.
edly or not. A part of the answer was found when (+)-hy-
droxyl pinanediol borate[28] was used as a hydroxy group
source. The branched isomer was obtained in a poor yield
(35%) but with a slight enantiomeric excess (11%), which is
in favor of a boron-containing nucleophile.
Conclusion
In conclusion, we have developed a straightforward, new
synthesis of substituted branched allylic alcohols from linear
allylic carbonates or halides by ruthenium-catalyzed allylic
substitution using a boronic acid as the nucleophile. This
process is the first example of nucleophilic allylic substitu-
tion by a hydroxy group delivered by a boronic acid in
ruthenium catalysis. A preliminary investigation concerning
the enantioselective addition of a hydroxy group onto a p-
allyl intermediate was also described. Even though the
enantioselectivities remained moderate (below 45%), this
procedure opens new opportunities in organic chemistry. We
are looking forward to extending this approach to other
types of reactions.
À
nium catalyst to give the product resulting from C C bond
formation as already suggested in the literature.[27] However,
under these reaction conditions, the hydroxy group transfer
from the boron species onto the electrophilic ruthenium(IV)
p-allyl intermediate is probably favored. The subsequent
question is if the migration and addition took place concert-
Experimental Section
General remarks: [Cp*Ru
C
Scheme 4. A plausible reaction pathway.
Chem. Eur. J. 2008, 14, 5630 – 5637
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
5633

J.-L. Renaud, F. Carreaux et al.
oven-dried glassware under an argon atmosphere. Tetrahydrofuran
(THF) was distilled from deep blue solutions of sodium/benzophenone
ketyl prior to use. CH2Cl2 was distilled from CaH2. Unless otherwise
stated, all reagents were used as received. Most of the reactions were
monitored by TLC on pre-coated silica plates (Merck 60 F254 0.25 mm).
Silica gel 60F254 was used for column flash chromatography. NMR spec-
tra were recorded in CDCl3 on a 300 or 200 MHz spectrometer operating
in the Fourier transform mode. The following abbreviation are used in re-
porting data: s, singlet; br s, broad singlet; d, doublet; t, triplet; q, quar-
tet; dt, doublet of triplets; dd, doublet of doublets; ddd, doublet of dou-
blets of doublets; m, multiplet. 13C NMR spectra were obtained with
broadband proton decoupling. Chemical shifts were recorded relative to
the internal tetramethylsilane (TMS) reference signal. Coupling constants
(J) are given in Hz. Melting points are uncorrected. High resolution mass
spectra (HRMS) were performed by the Centre RØgional de Mesures
Physiques de l’Ouest.
1.30 ppm (t, J=7.5 Hz, 3H; CO2CH2CH3); 13C NMR (75 MHz, CDCl3)
166.9, 141.5, 133.6, 131.8, 131.4, 130.4, 128.7, 126.8, 126.2, 125.4, 125.0,
123.4, 120.9, 60.6, 14.4 ppm.
(E)-Ethyl-3-(2,4,6-trimethylphenyl)acrylate:[30,34]
86%.
1H NMR
(200 MHz, CDCl3): d= 7.90 (d, J=16.4 Hz, 1H; CH=CH), 6.10 (d, J=
16.4 Hz, 1H; CH=CH), 6.60 (s, 2H), 4.30 (q, J=7.1 Hz, 2H;
CO2CH2CH3) 2.30 (s, 9H; 3CH3), 1.30 ppm (t, J=7.1 Hz, 3H;
CO2CH2CH3); 13C NMR (50 MHz, CDCl3): d=168.0, 139.2, 137.0, 135.2,
131.9, 126.8 (2C), 117.8, 59.6, 24.0, 21.0 (2C), 14.8 ppm.
(E)-Ethyl-3-(2,4,6-trimethoxyphenyl)acrylate:[33]
96%.
1H NMR
(200 MHz, CDCl3): d= 8.10 (d, J=16.2 Hz, 1H; CH=CH), 6.80 (d, J=
16.2 Hz, 1H; CH=CH), 6.10 (s, 2H), 4.30 (q, J=7.1 Hz, 2H;
CO2CH2CH3), 3.85 (s, 9H;
3 OCH3), 1.30 ppm (t, J=7.1 Hz, 3H;
CO2CH2CH3); 13C NMR (50 MHz, CDCl3): d= 170.0, 163.0, 161.6 (2C),
135.9, 117.8, 106.0, 90.8 (2C), 60.3, 56.1 (3C), 14.9 ppm.
(E)-Ethyl-3-(4-(N,N-dimethylamino)phenyl)acrylate:[29] 94%. 1H NMR
(200 MHz, CDCl3): d= 7.65 (d, J=15.9 Hz, 1H; CH=CH), 7.45 (d, J=
8.8 Hz, 2H), 6.70 (d, J=8.8 Hz, 2H), 6.25 (d, J=15.9 Hz, 1H; CH=CH),
4.26 (q, J=7.0 Hz, 2H; CO2CH2CH3), 3.04 (s, 6H; 2 CH3), 1.35 ppm (t,
J=7.0 Hz, 3H; CO2CH2CH3); 13C NMR (50 MHz, CDCl3): d= 168.8,
150.6, 136.9, 127.9 (2C), 124.4, 117.8, 112.7 (2C), 60.3, 40.8 (2C),
14.9 ppm.
(E)-Ethyl-3-(4-benzyloxy)phenyl)acrylate:[31] 84%. 1H NMR (200 MHz,
CDCl3): d= 7.67 (d, J=16.0 Hz, 1H; CH=CH), 7.6–7.4 (m, 7H), 7.00 (d,
J=8.7 Hz, 2H), 6.33 (d, J=16.0 Hz, 1H; CH=CH), 5.12 (s, 2H; H12),
4.28 (q, J=7.2 Hz, 2H; CO2CH2CH3), 1.36 ppm (t, J=7.2 Hz, 3H;
CO2CH2CH3); 13C NMR (50 MHz, CDCl3): d=168, 159.2, 140.0, 137.0,
132.1 (2C), 129.0, 128.5 (2C), 129.8, 127.6 (2C), 117.5, 115.7 (2C), 75.2,
44.7, 13.8 ppm.
(E)-Ethyl-3-(4-methoxyphenyl)acrylate:[29] 86%. 1H NMR (200 MHz,
CDCl3): d=7.70 (d, J=16.0 Hz, 2H; CH=CH), 7.55–7.35 (m, 2H), 6.90–
6.70 (m, 2H), 6.40 (d, J=16.0 Hz, 1H; CH=CH), 4.20 (q, J=7.1 Hz, 2H;
CO2CH2CH3), 1.30 ppm (t, J=7.1 Hz, 3H; CO2CH2CH3); 13C NMR
(50 MHz, CDCl3): d=167.0, 164.0, 144.0, 130.1, 127.5 (2C), 116.0, 114.7
(2C), 60.7, 56.0, 14.8 ppm.
General procedure for the synthesis of unsaturated ester: In a Schlenk
tube, LiCl (33.1 mmol, 1.1 equiv) was dried under vacuum, and acetoni-
trile (100 mL) was added. The reaction mixture was cooled to 08C and
triethylphosphonoacetate (30.1 mmol, 1 equiv) in acetonitrile (100 mL)
and aldehyde (30.1 mmol, 1 equiv) were added. After 5 min,
diazabicyclo[5.4.0]undec-7-ene (30.1 mmol, 1 equiv) was added. The reac-
A
tion mixture was warmed to room temperature and stirred overnight.
Then, the solution was diluted in diethyl ether and washed with a saturat-
ed solution of ammonium chloride, brine, and dried over MgSO4, filtered
on celite and concentrated. The crude product was purified on silica gel
by flash chromatography (Hept/Et2O: 7/3, Hept=heptane, Et=ethyl) to
give the corresponding unsaturated ester in good yield.
(E)-Ethyl-3-(2-nitrophenyl)acrylate:[29]
94%.
1H NMR (200 MHz,
CDCl3): d=8.20–7.60 (m, 4H), 8.10 (d, J=16.1 Hz, 1H; CH=CH), 6.55
(d, J=16.1 Hz, 1H; CH=CH), 4.20 (q, J=7.0 Hz, 2H; CO2CH2CH3),
1.30 ppm (t, J=7.0 Hz, 3H; CO2CH2CH3); 13C NMR (50 MHz, CDCl3):
d=166.8, 142.6, 141.1, 135.6, 128.9, 127.3, 126.9, 123.8, 115.2, 61.2,
14.7 ppm.
(E)-Ethyl-3-(3-nitrophenyl)acrylate:[30]
96%.
1H NMR (200 MHz,
CDCl3): d=8.38 (s, 1H), 8.25 (d, J=7.6 Hz, 1H; H9), 7.85 (d, J=7.7 Hz,
1H), 7.65–7.50 (m, 1H), 7.75 (d, J=16.1 Hz, 1H; CH=CH), 6.55 (d, J=
16.1 Hz, 1H; CH=CH), 4.20 (q, J=7.2 Hz, 2H; CO2CH2CH3), 1.30 ppm
(t, J=7.2 Hz, 3H, CO2CH2CH3); 13C NMR (50 MHz, CDCl3): d=166.9,
149.1, 142.4, 136.5, 134, 130.4, 124.2, 122.9, 121.3, 59.5, 14.7 ppm.
General procedure for the synthesis of allylic alcohol: To a solution of
ester (10 mmol, 1 equiv) in toluene (70 mL), diisobutylaluminum hydride
(2 equiv) was slowly added at À788C. The reaction mixture was stirred at
this temperature until completion, checked by TLC monitoring. Then,
the resulting solution was diluted in dichloromethane (70 mL) and a suit-
able quantity of a saturated solution of Na2SO4 was added to precipitate
the aluminum salts. This was then dried over MgSO4, filtered, and con-
centrated under vacuum. The crude product was purified on silica gel by
flash chromatography (Hept/Et2O: 7/3) to yield the corresponding allylic
alcohol.
(E)-Ethyl-3-(4-nitrophenyl)acrylate:[29]
95%.
1H NMR (200 MHz,
CDCl3): d=8.30 (d, J=8.8 Hz, 2H), 7.70 (d, J=8.8 Hz, 2H), 7.80 (d, J=
16.1 Hz, 1H; CH=CH), 6.60 (d, J=16.1 Hz, 1H; CH=CH), 4.30 (q, J=
7.0 Hz, 2H; CO2CH2CH3), 1.30 ppm (t, J=7.0 Hz, 3H; CO2CH2CH3);
13C NMR (50 MHz, CDCl3): d=166.8, 148.9, 142.1, 139.6, 129.0, 124.6,
123.0, 61.5, 14.7 ppm.
(E)-3-(2-Nitrophenyl)prop-2-en-1-ol:[18, 36] 78%. 1H NMR (200 MHz,
CDCl3): d= 8.00 (d, J=8.2 Hz, 1H; H6), 7.70–7.40 (m, 3H), 7.20 (d, J=
15.9 Hz, 1H; CH=CHCH2), 6.40 (m, CH=CHCH2, 1H), 4.40 (d, J=
6.0 Hz, 2H; CH2OH), 3.05 ppm (br. s, 1H; OH); 13C NMR (50 MHz,
CDCl3): d=148.2, 134.7, 133.6, 132.9, 129.2, 128.5, 125.9, 124.7, 63.5 ppm.
(E)-3-(3-Nitrophenyl)prop-2-en-1-ol:[37] 97%. 1H NMR (200 MHz,
CDCl3): d=8.25 (s, 1H), 8.10 (d, J=7.7 Hz, 1H), 7.70 (d, J=7.5 Hz,
1H), 7.50 (m, 1H), 6.75 (d, J=16.1 Hz, 1H; CH=CHCH2), 6.50 (m, 1H;
CH=CHCH2), 4.35 (d, J=6.0 Hz, 2H; CH2OH), 2.70 ppm (br. s, 1H;
OH); 13C NMR (50 MHz, CDCl3): d=148.3, 144.5, 130.8, 128.7, 125.8,
124.2, 123.2, 121.3, 63.7 ppm.
(E)-3-(4-Nitrophenyl)prop-2-en-1-ol:[18, 39] 98%. 1H NMR (200 MHz,
CDCl3): d= 8.20 (d, J=8.6 Hz, 2H), 7.60 (d, J=8.6 Hz, 2H), 7.75 (d, J=
16.1 Hz, 1H; CH=CHCH2), 6.57 (m, 1H; CH=CHCH2), 4.30 (d, J=
6.0 Hz, 2H; CH2OH), 3.10 ppm (br. s, 1H; OH); 13C NMR (50 MHz,
CDCl3): d=147.3, 144.5, 128.6, 127.4 (2C), 124.5, 123.0 (2C), 63.5 ppm.
(E)-3-(4-Chlorophenyl)prop-2-en-1-ol:[35] 98%. 1H NMR (300 MHz,
CDCl3): d= 7.25–7.18 (m, 4H), 6.47 (d, J=15.9 Hz, 1H; CH=CH), 6.29
(dt, J=15.9 Hz, J=5.3 Hz, 1H; CH=CHCH2), 4.26 (d, J=5.3 Hz, 2H;
CH2OH), 3.97 ppm (br. s, 1H; OH); 13C NMR (75 MHz, CDCl3): d=
135.1, 132.8, 129.7, 129.1 (2C), 128.7, 127.7 (2C), 63.5 ppm.
(E)-Ethyl-3-(4-chlorophenyl)acrylate:[29] 91%. 1H NMR (300 MHz,
CDCl3): d=7.57 (d, J=15.8 Hz, 1H; CH=CH), 7.40 (d, J=8.2 Hz, 2H;
H7, H11), 7.31 (d, J=8.2 Hz, 2H; H8, H10), 6.36 (d, J=15.8 Hz, 1H; CH=
CH), 4.22 (q, J=6.7 Hz, 2H; CO2CH2CH3), 1.28 ppm (t, J=6.7 Hz, 3H;
CO2CH2CH3); 13C NMR (75 MHz, CDCl3): d=165.9, 142.5, 135.6 (2C),
130.5, 129.0 (2C), 128.8, 118.6, 60.1, 14.0 ppm.
(E)-Ethyl-3-(4-bromophenyl)acrylate:[29] 85%. 1H NMR (300 MHz,
CDCl3): d= 7.65 (d, J=16.0 Hz, 1H; CH=CH), 7.45 (d, J=8.4 Hz, 2H),
7.30 (d, J=8.4 Hz, 2H), 6.45 (d, J=16.0 Hz, 1H; CH=CH), 4.20 (q, J=
7.2 Hz, 2H; CO2CH2CH3), 1.30 ppm (t, J=7.2 Hz, 3H; CO2CH2CH3);
13C NMR (75 MHz, CDCl3): d= 167.1, 143.6, 133.8, 132.5 (2C), 129.8
(2C), 124.9, 119.4, 61.1, 14.8 ppm.
(E)-Ethyl-3-(naphthalen-2-yl)acrylate:[29] 99%. 1H NMR (200 MHz,
CDCl3): d=8.50 (d, J=15.8 Hz, 1H; CH=CH), 8.30–7.40 (m, 7H), 6.50
(d, J=15.8 Hz, 1H; CH=CH), 4.30 (q, J=7.1 Hz, 2H; CO2CH2CH3),
1.30 ppm (t, J=7.1 Hz, 3H; CO2CH2CH3); 13C NMR (50 MHz, CDCl3):
d=167.4, 142.1, 134.1, 132.5 (2C), 130.0, 129.2, 127.3, 126.6, 125.9, 125.4,
123.8, 121.4, 61.1, 14.8 ppm.
(E)-Ethyl-3-(naphthalen-1-yl)acrylate:[32] 92%. 1H NMR (300 MHz,
CDCl3): d= 8.47 (d, J=15.7 Hz, 1H; CH=CH), 8.08–7.24 (m, 7H), 6.46
(d, J=15.7 Hz, 1H; CH=CH), 4.28 (q, J=7.5 Hz, 2H; CO2CH2CH3),
5634
www.chemeurj.org
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2008, 14, 5630 – 5637

Allylic Alcohols
FULL PAPER
(E)-3-(4-Bromophenyl)prop-2-en-1-ol:[38] 74%. 1H NMR (300 MHz,
CDCl3): d=7.45 (d, J=8.5 Hz, 2H), 7.25 (d, J=8.5 Hz, 2H), 6.60 (d, J=
16.0 Hz, 1H; CH=CH), 6.35 (m, CH=CHCH2, 1H), 4.35 (d, J=5.1 Hz,
2H; CH2OH), 3.00 ppm (br. s, 1H; OH); 13C NMR (75 MHz, CDCl3):
d=136.1, 132.1 (2C), 129.7, 128.4 (2C), 123.1, 121.8, 63.9 ppm.
6.4 Hz, 2H; CH2Cl); 13C NMR (50 MHz, CDCl3): d=147.5, 140.8, 130.8,
127.4 (2C), 123.4, 123.0 (2C), 45.8 ppm.
(E)-1-(3-Chloroprop-1-enyl)-4-chlorobenzene:[41] 1H NMR (300 MHz,
CDCl3): d=7.41–7.28 (m, 4H), 6.60 (d, J=16.5 Hz, 1H; CH=CHCH2),
6.31 (m, 1H; CH=CHCH2), 4.26 ppm (dd, J=7.1 Hz, J=1.0 Hz, 2H;
CH2Cl); 13C NMR (50 MHz, CDCl3): d=134.8, 132.3, 131.5, 128.2 (2C),
127.6 (2C), 124.8, 45.3 ppm.
(E)-3-(2,4,6-Trimethylphenyl)prop-2-en-1-ol:[34]
87%.
1H NMR
(200 MHz, CDCl3): d= 6.90 (s, 2H), 6.65 (d, J=16.2 Hz, 1H; CH=
CHCH2), 5.95 (m, 1H; CH=CHCH2), 4.40 (d, J=6.0 Hz, 2H; CH2OH),
3.40 (br. s, 1H; OH), 2.30 ppm (s, 9H; 3 CH3); 13C NMR (50 MHz,
CDCl3): d=137.0, 136.0 (2C), 134.0, 130.0, 129.0 (2C), 124.0, 65.0, 26.0,
21.0 ppm (2C).
(E)-1-(3-Chloroprop-1-enyl)-4-bromobenzene:
1H NMR
(300 MHz,
CDCl3): d=7.45 (d, J=8.5 Hz, 2H), 7.25 (d, J=8.5 Hz, 2H), 6.65 (d, J=
15.7 Hz, 1H; CH=CHCH2), 6.35 (m, 1H; CH=CHCH2), 4.26 ppm (d, J=
7.0 Hz, 2H; CH2Cl); 13C NMR (50 MHz, CDCl3): d=135.2, 132.1 (2C),
129.7, 128.4 (2C), 124.2, 122.6, 45.6 ppm.
(E)-3-(2,4,6-Trimethoxyphenyl)prop-2-en-1-ol:[33]
99%.
1H NMR
(E)-2-(3-Chloroprop-1-enyl)-1,3,5-trimetylbenzene: 1H NMR (200 MHz,
CDCl3): d=6.90 (s, 2H), 6.65 (d, J=16.0 Hz, 1H; CH=CHCH2), 5.85 (m,
1H; CH=CHCH2), 4.30 (d, J=7.0 Hz, 2H; CH2Cl), 2.30 ppm (s, 9H;
3CH3); 13C NMR (50 MHz, CDCl3): d=137.0, 136.2 (2C), 132.3, 129.4,
128.6 (2C), 123.8, 46.7, 26.0, 20.8 ppm (2C).
(200 MHz, CDCl3): d=6.90 (d, J=16.1 Hz, 1H; CH=CHCH2), 6.70 (m,
1H; CH=CHCH2), 6.10 (s, 2H), 4.40 (d, J=5.6 Hz, 2H; CH2OH), 3.85 (s,
9H; 3OCH3), 2.50 ppm (br. s, 1H; OH); 13C NMR (50 MHz, CDCl3): d=
159.0 (3C), 129.2, 122.3, 107.0, 91.0 (2C), 65.9, 56.1 ppm (3C).
(E)-3-{4-(N,N-Dimethylamino)phenyl}prop-2-en-1-ol:[39] 99%. 1H NMR
(200 MHz, CDCl3): d=7.30 (d, J=8.7 Hz, 2H), 6.70 (d, J=8.7 Hz, 2H),
6.65 (d, J=16.2 Hz, 1H; CH=CHCH2), 6.20 (m, 1H; CH=CHCH2), 4.30
(d, J=6.3 Hz, 2H; CH2OH), 3.00 (s, 6H; 2CH3), 2.30 ppm (br. s, 1H;
OH); 13C NMR (50 MHz, CDCl3): d=150.6, 132.3, 127.9 (2C), 125.4,
124.4, 112.7 (2C), 64.7, 40.9 ppm (2C).
(E)-2-(3-Chloroprop-1-enyl)-1,3,5-trimethoxybenzene:
1H NMR
(200 MHz, CDCl3): d=6.90 (d, J=16.0 Hz, 1H; CH=CHCH2), 6.67 (m,
1H; CH=CHCH2), 6.10 (s, 2H), 4.30 (d, J=7.0 Hz, 2H; CH2Cl),
3.85 ppm (s, 9H; 3 OCH3); 13C NMR (50 MHz, CDCl3): d=160.1, 159.0
(2C), 131.0, 122.7, 105.0, 92.9 (2C), 56.1 (3C), 43.5 ppm.
(E)-3-(4-(Benzyloxy)phenyl)prop-2-en-1-ol:[40] 99%. 1H NMR (200 MHz,
CDCl3): d= 7.50 (m, 7H), 6.96 (d, J=8.5 Hz, 2H), 6.59 (d, J=15.8 Hz,
1H; CH=CHCH2), 6.30 (m, 1H; CH=CHCH2), 5.10 (s, 2H; H10), 4.33 (d,
J=6.2 Hz, 2H; CH2OH), 3.10 ppm (br. s, 1H; OH); 13C NMR (50 MHz,
CDCl3): d=159.0, 137.3, 131.0 (2C), 130.0, 129.0, 128.5 (2C), 128.0, 127.6
(2C), 126.9 (C2), 115.7 (2C), 70.4, 64.4 ppm.
(E)-4-(3-Chloroprop-1-enyl)-N,N-dimethylbenzenamine:
1H NMR
(200 MHz, CDCl3): d=7.30 (d, J=8.8 Hz, 2H), 6.80 (d, J=8.8 Hz, 2H),
6.65 (d, J=16.2 Hz, 1H; CH=CHCH2), 6.25 (m, 1H; CH=CHCH2), 4.20
(d, J=6.3 Hz, 2H; CH2Cl), 3.00 ppm (s, 6H; 2CH3); 13C NMR (50 MHz,
CDCl3): d=148.6, 132.3, 127.9 (2C), 125.0, 124.0, 114.1 (2C), 46.7,
40.9 ppm (2C).
(E)-3-(4-(Methoxyphenyl)prop-2-en-1-ol:[35] 87%. 1H NMR (200 MHz,
CDCl3): d=7.40–7.25 (m, 2H), 6.95–6.85 (m, 2H), 6.60 (d, J=15.9 Hz,
1H; CH=CHCH2), 6.25 (m, 1H; CH=CHCH2), 4.30 (d, J=5.8 Hz, 2H;
CH2OH), 3.85 (s, 3H; OCH3), 2.90 ppm (br. s, 1H; OH); 13C NMR
(50 MHz, CDCl3): d=159.6, 129.9, 128.1, 126.7 (2C), 126.1, 114.4 (2C),
64.2, 55.7 ppm.
(E)-1-(Benzyloxy)-4-(3-chloroprop-1-enyl)benzene: 1H NMR (200 MHz,
CDCl3): d=7.55–7.25 (m, 7H), 7.10 (d, J=8.5 Hz, 2H), 6.68 (d, J=
15.9 Hz, 1H; CH=CHCH2), 6.20 (m, 1H; CH=CHCH2), 5.10 (s, 2H;
H10), 4.20 ppm (d, J=6.2 Hz, 2H; CH2Cl); 13C NMR (50 MHz, CDCl3):
d=160.0, 140.2, 132.0, 131.0 (2C), 129.0, 128.7 (2C), 128.1 (2C), 126.0,
124.1, 113.9 (2C), 70.4, 44.9 ppm.
(E)-3-(Naphthalen-2-yl)prop-2-en-1-ol:[35] 93%. 1H NMR (200 MHz,
CDCl3): d=8.10–7.40 (m, 7H), 7.20 (d, J=15.9 Hz, 1H; CH=CHCH2),
6.40 (m, 1H; CH=CHCH2), 4.45 ppm (d, J=6.1 Hz, 2H; CH2OH);
13C NMR (50 MHz, CDCl3): d=133.5, 133.0, 132.0, 131.1, 128.8, 128.2,
127.9, 127.6, 126.4, 126.2, 125.8, 123.5, 63.7 ppm.
(E)-1-(3-Chloroprop-1-enyl)-4-methoxybenzene:[41] 1H NMR (200 MHz,
CDCl3): d=7.30 (m, 2H), 6.90 (m, 2H), 6.60 (d, J=15.6 Hz, 1H; CH=
CHCH2), 6.20 (m, 1H; CH=CHCH2), 4.20 (d, J=7.3 Hz, 2H; CH2Cl),
3.85 ppm (s, 3H; OCH3); 13C NMR (50 MHz, CDCl3): d=160.1, 130.2,
126.9 (3C), 123.1, 114.4 (2C), 55.8, 46.9 ppm.
(E)-3-(Naphthalen-1-yl)prop-2-en-1ol:[35] 90%. 1H NMR (300 MHz,
CDCl3): d=8.13 (d, J=9.1 Hz, 1H), 7.87–7.80 (m, 2H), 7.64–7.38 (m,
5H; CH=CHCH2), 6.47 (dt, J=15.6 Hz, J=5.6 Hz, 1H), 4.47 (dd, J=
5.6 Hz, J=1.4 Hz, 2H; CH2OH), 3.42 ppm (br. s, 1H; OH); 13C NMR
(75 MHz, CDCl3): d=133.6, 133.5, 131.7, 131.2, 128.5, 128.2, 128.0, 126.0,
125.8, 125.6, 123.9, 123.7, 63.9 ppm.
(E)-2-(3-Chloroprop-1-enyl)naphthalene: 1H NMR (200 MHz, CDCl3):
d=8.10–7.40 (m, 7H), 7.20 (d, J=15.9 Hz, 1H; CH=CHCH2), 6.40 (m,
1H; CH=CHCH2), 4.30 ppm (d, J=7.0 Hz, 2H; CH2Cl); 13C NMR
(50 MHz, CDCl3): d=135.0, 134.8, 134.0, 130.0 (2C), 129.0 (2C), 127.6,
126.8, 125.0, 124.0 (2C), 46.0 ppm.
(E)-1-(3-Chloroprop-1-enyl)naphthalene: 1H NMR (300 MHz, CDCl3):
d=8.11 (d, J=7.2 Hz, 1H), 7.91–7.83 (m, 2H), 7.65–7.43 (m, 5H), 6.37
(dt, J=15.4 Hz, J=7.1 Hz, 1H; CH=CHCH2), 4.38 ppm (dd, J=7.1 Hz,
J=1.1 Hz, 2H; CH2Cl); 13C NMR (75 MHz, CDCl3): d=133.6, 133.5,
131.2, 131.1, 128.7, 128.6, 128.0, 126.2, 125.9, 125.5, 124.2, 123.6, 45.5 ppm.
General procedure for the synthesis of allylic chloride: To a solution of
allylic alcohol (1 equiv) in diethyl ether (1 mmolmLÀ1), SOCl2 (1 equiv)
was slowly added at 08C. The reaction mixture was stirred until comple-
tion, as determined by TLC. Then, the resulting solution was diluted with
dichloromethane, washed with a saturated solution of NaHCO3 and then
brine, and then dried over Na2SO4, filtered, and concentrated. The allylic
chloride was used without further purifications.
General procedure for the allylic substitution catalyzed by ruthenium
complex: In a Schlenk tube under argon, allylic chloride (0.5 mmol,
1 equiv), phenylboronic acid (0.6 mmol, 1.2 equiv), K2CO3 (1.2 equiv),
(E)-1-(3-Chloroprop-1-enyl)-2-nitrobenzene:[41]
1H NMR
(200 MHz,
[Cp*Ru(MeCN)3]PF6 (2; 3 mol%) and acetonitrile (1 mL) were added.
G
CDCl3): d=8.10 (d, J=8.1 Hz, 1H), 7.90 (m, 1H), 7.70 (m, 1H), 7.48 (m,
1H), 7.25 (d, J=15.5 Hz, 1H; CH=CHCH2), 6.25 (m, 1H; CH=CHCH2),
4.30 ppm (d, J=6.9 Hz, 2H; CH2Cl); 13C NMR (50 MHz, CDCl3): d=
148.0, 133.7, 132.4 , 129.0, 128.6, 127.9, 124.7, 123.8, 45.9 ppm.
The reaction mixture was stirred for 24 h at room temperature. The
crude product was purified on silica gel by flash chromatography (Hept/
Et2O: 9/1) to furnish linear and branched allylic product.
1-Phenylprop-2-en-1-ol:[42] 1H NMR (200 MHz, CDCl3): d=7.50–7.25 (m,
5H), 6.10 (ddd, J=16.4 Hz, J=10.2 Hz, J=6.0 Hz, 1H; CH=CH2), 5.40
(m, 1H; CH=CH2), 5.20–5.10 (m, 2H; CH=CH2, CHOH), 3.10 ppm (br.
s, 1H; OH); 13C NMR (50 MHz, CDCl3): d=141.4, 138.5, 128.3, 127.4,
126.2, 116.2, 76.8 ppm.
1-(2-Nitrophenyl)prop-2-en-1-ol:[42] 1H NMR (300 MHz, CDCl3): d=7.95
(dd, J=8.1 Hz, J=0.9 Hz, 1H), 7.77 (m, 1H), 7.63 (m, 1H), 7.40 (m,
1H), 6.05 (ddd, J=17.1 Hz, J=10.4 Hz, J=5.3 Hz, 1H; CH=CH2), 5.71
(d, J=5.3 Hz, 1H; CHOH), 5.35 (dd, J=17.1 Hz, J=1.1 Hz, 1H; CH=
CH2), 5.22 (dd, J=10.4 Hz, J=1.1 Hz, 1H; CH=CH2), 3.20 ppm (br s.,
(E)-1-(3-Chloroprop-1-enyl)-3-nitrobenzene:[41]
1H NMR
(200 MHz,
CDCl3): d=8.25 (s, 1H), 8.10 (d, 1H; J=8.1 Hz), 7.70 (d, 1H; J=
7.8 Hz), 7.53 (m, 1H), 6.75 (d, J=15.7 Hz, 1H; CH=CHCH2), 6.55 (m,
1H; CH=CHCH2), 4.20 ppm (d, J=7.2 Hz, 2H; CH2Cl); 13C NMR
(50 MHz, CDCl3): d=138.0, 132.9, 132.3, 130.0, 128.9, 123.3, 122.4, 121.7,
32.4 ppm.
(E)-1-(3-Chloroprop-1-enyl)-4-nitrobenzene:[41]
1H NMR
(200 MHz,
CDCl3): d=8.20 (d, J=8.3 Hz, 2H), 7.60 (d, J=8.3 Hz, 2H), 6.80 (d, J=
15.7 Hz, 1H; CH=CHCH2), 6.53 (m, 1H; CH=CHCH2), 4.30 ppm (d, J=
Chem. Eur. J. 2008, 14, 5630 – 5637
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
5635

J.-L. Renaud, F. Carreaux et al.
1H; OH); 13C NMR (75 MHz, CDCl3): d=148.2, 138.1, 137.6, 133.6,
128.8, 128.4, 124.5, 116.1, 69.8 ppm.
Synthesis of sodium phenylboronate: Phenylboronic acid (1 g, 8.2 mmol)
was dissolved in a minimal amount of warm toluene under stirring, and a
saturated aqueous sodium hydroxide solution was added dropwise until
no further precipitate formed. The precipitate obtained was filtered off
and washed with warm toluene to give the pure salt as a colorless solid
(1.14 g, 86%). M.p. >2758C. 1H NMR (200 MHz, D2O ref. CH3CN): d=
1-(3-Nitrophenyl)prop-2-en-1-ol:[42] 1H NMR (200 MHz, CDCl3): d=8.25
(m, 1H; H5), 8.10 (m, 1H), 7.70 (m, 1H9), 7.57 (m, 1H), 6.05 (m, 1H;
CH=CH2), 5.40 (dt, J=17.1 Hz, J=1.2 Hz, 1H; CH=CH2), 5.30 (d, J=
6.7 Hz, 2H; CHOH), 5.28 (dt, J=10.4 Hz, J=1.2 Hz, 1H; CH=CH2),
2.50 ppm (br. s, 1H; OH); 13C NMR (50 MHz, CDCl3): d=148.2, 138.1,
137.7, 133.7, 128.9, 128.5, 124.6, 118.7, 116.2, 69.4 ppm.
1-(4-Nitrophenyl)prop-2-en-1-ol:[42] 1H NMR (200 MHz, CDCl3): d=8.20
(d, J=8.6 Hz, 2H), 7.60 (m, 2H), 6.00 (m, 1H; CH=CH2), 5.40 (dt, J=
17.4 Hz, J=1.1 Hz, 1H; CH=CH2), 5.30 (d, J=6.7 Hz, 1H; CHOH), 5.22
(dt, J=10.4 Hz, J=1.1 Hz, 1H; CH=CH2), 2.20 ppm (br. s, 1H; OH);
13C NMR (50 MHz, CDCl3): d=149.5, 147.3, 139.5, 127.1, 123.7, 116.4,
74.7 ppm.
1-(4-Chlorophenyl)prop-2-en-1-ol: 1H NMR (300 MHz, CDCl3): d=7.34–
7.26 (m, 4H), 6.09 (ddd, J=17.2 Hz, J=10.2 Hz, J=6.3 Hz, 1H; CH=
CH2), 5.39 (ddd, J=17.2 Hz, J=2.5 Hz, J=1.3 Hz, 1H; CH=CH2), 5.24–
5.18 (m, 2H; CH=CH2, CHOH), 3.04 ppm (br. s, 1H; OH); 13C NMR
(75 MHz, CDCl3): d=141.1, 139.2, 134.0, 129.1, 128.7, 115.6, 74.7 ppm.
7.58 (d, J=7.9 Hz, 2H; H3, H5), 7.21–7.05 ppm (m, 3H; H aromatics);
13
À
C NMR (50 MHz, D2O ref. CH3CN) (C B is not observed): d=131.3
(C3, C5), 127.3 (C2, C6), 119.1 ppm (C4); 11B NMR (96 MHz, D2O): d=
3.2 ppm.
Acknowledgement
We thank Paul Le Maux for his technical assistance. The University of
Rennes 1 and UMR 6226 are gratefully acknowledged for financial sup-
port.
1-(4-Bromophenyl)prop-2-en-1-ol:[43] 1H NMR (300 MHz, CDCl3): d=
7.50 (d, J=8.4 Hz, 2H), 7.25 (d, J=8.4 Hz, 2H), 5.96 (ddd, J=17.1 Hz,
J=10.3 Hz, J=6.1 Hz, 1H; CH=CH2), 5.35 (ddd, J=17.1 Hz, J=2.6 Hz,
J=1.3 Hz, 1H; CH=CH2), 5.20 (ddd, J=10.3 Hz, J=2.3 Hz, J=1.3 Hz,
1H; CH=CH2), 3.05 ppm (br. s, 1H; OH); 13C NMR (75 MHz, CDCl3):
d=141.5, 139.7, 131.5, 128.6, 121.5, 115.6, 74.6 ppm.
1-Mesitylprop-2-en-1-ol: M.p. 52–548C. 1H NMR (300 MHz, CDCl3): d=
6.90 (s, 2H), 6.15 (ddd, J=17.3 Hz, J=10.5 Hz, J=4.5 Hz, 1H; CH=
CH2), 5.72 (m, 1H; CHOH), 5.22 (ddd, J=17.3 Hz, J=3.5 Hz, J=1.7 Hz,
1H; CH=CH2), 5.18 (ddd, J=10.5 Hz, J=4.5 Hz, J=1.7 Hz, 1H; CH=
CH2), 3.05 (br. s, 1H; OH), 2.39 (s, 6H; 2CH3), 2.30 ppm (s, 3H; CH3);
13C NMR (75 MHz, CDCl3): d=138.6, 136.5, 134.9 (2C), 130.0 (2C),
114.3, 71.5, 20.7 (CH3), 20.5 ppm (2CH3); HRMS (EI): m/z: calcd for
C12H16O: 176.1212; found: 176.1208.
1-(Naphthalen-2-yl)prop-2-en-1-ol:[44] 1H NMR (200 MHz, CDCl3): d=
8.10–7.80 (m, 4H), 7.50–7.40 (m, 3H), 6.25 (m, 1H; CH=CH2), 5.45–5.35
(m, 2H; CHOH, CH=CH2), 5.20 (m, 1H; CH=CH2), 2.20 ppm (br. s, 1H;
OH); 13C NMR (50 MHz, CDCl3): d=140.0, 139.6, 133.1, 132.8, 128.1,
127.9, 127.5, 126.0, 125.8, 124.8, 124.4, 115.4, 75.5 ppm.
1-(Naphthalen-1-yl)prop-2-en-1-ol:[43] 1H NMR (300 MHz, CDCl3): d=
8.23 (d, J=9.1 Hz, 1H), 7.90–7.80 (m, 2H;), 7.66–7.50 (m, 4H), 6.27
(ddd, J=17.3 Hz, J=10.3 Hz, J=5.3 Hz, 1H; CH=CH2), 5.97 (d, J=
5.3 Hz, 1H; CHOH), 5.48 (ddd, J=17.3 Hz, J=2.4 Hz, J=1.3 Hz, 1H;
CH=CH2), 5.30 (ddd, J=10.4 Hz, J=2.4 Hz, J=1.2 Hz, 1H; CH=CH2),
2.18 ppm (br. s, 1H; OH); 13C NMR (75 MHz, CDCl3): d=139.6, 138.0,
133.9, 130.6, 128.8, 128.5, 126.0, 125.6, 125.4, 123.9, 123.7, 115.6, 72.3 ppm.
1-(2,4,6-Trimethoxyphenyl)propan-1-one: 1H NMR (300 MHz, CDCl3):
d=6.10 (s, 2H), 3.85 (s, 9H; 3OCH3), 2.95 (q, J=7.3 Hz, 2H;
COCH2CH3), 1.20 ppm (t, J=7.3 Hz, 3H; COCH2CH3); 13C NMR
(75 MHz, CDCl3): d=205.3, 162.1, 158.0, 113.5, 90.5, 55.8 (2 OCH3), 55.4
(OCH3), 38.0, 7.9 ppm.
1-(4-Methoxyphenyl)propane-1-one:[47] 1H NMR (200 MHz, CDCl3): d=
7.93 (d, J=8.8 Hz, 2H), 6.95 (d, J=8.8 Hz, 2H), 3.87 (s, 3H; OCH3),
2.95 (q, J=7.2 Hz, 2H), 1.24 ppm (t, J=7.2 Hz, 3H; COCH2CH3);
13C NMR (50 MHz, CDCl3): d=199.5, 163.3, 130.1, 113.6, 55.4 (OCH3),
43.4, 8.4 ppm.
1-(4-Benzyloxyphenyl)propan-1-one:[46] 1H NMR (200 MHz, CDCl3): d=
8.0 (d, J=8.8 Hz, 2H; H5, H9), 7.50–7.30 (m, 5H), 7.00 (d, J=8.8 Hz,
2H), 5.10 (s, 2H), 2.95 (q, J=7.3 Hz, 2H; COCH2CH3), 1.20 ppm (t, J=
7.3 Hz, 3H; COCH2CH3); 13C NMR (50 MHz, CDCl3): d=202.4, 160.9,
136.1, 13.8, 128.9, 128.1, 127.4, 113.9, 69.9, 30.2, 7.3 ppm.
1-(4-N,N-Dimethylaminophenyl)propan-1-one:[45] 1H NMR (200 MHz,
CDCl3): d=8.0 (d, J=8.8 Hz, 2H), 6.95 (d, J=8.8 Hz, 2H), 3.00 (s, 6H;
2 CH3), 2.95 (q, J=7.2 Hz, 2H; COCH2CH3), 1.20 ppm (t, J=7.2 Hz,
3H; COCH2CH3); 13C NMR (50 MHz, CDCl3): d=201.7, 153.5, 130.8,
129.4, 110.4, 39.9 (CH3), 31.6, 7.6 ppm.
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Received: December 22, 2007
Revised: February 22, 2008
Published online: April 17, 2008
Chem. Eur. J. 2008, 14, 5630 – 5637
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
5637