FULL PAPERS

DOI: 10.1002/adsc.201100736

Efficient Procedures to Prepare Primary and Secondary Alkyl

Halides from Alkanols via the Corresponding Sulfonates under
Mild Conditions
Grard Cahiez,a,* Olivier Gager,a Alban Moyeux,a and Thomas Delacroixa
a
Department of Chemistry (UMR 7244), CNRS – Universit de Paris 13, 74 Rue Marcel Cachin, F-93017 Bobigny, France
E-mail: gerard.cahiez@univ-paris13.fr

Received: September 23, 2011; Revised: January 27, 2012; Published online: && &&, 0000

Dedicated to Professor Alfredo Ricci on the occasion of his retirement.

Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201100736.

Abstract: The study presented herein shows that sul-
fonate/halide exchange can be advantageously per-
formed in THF to avoid several side reactions such
as elimination and epimerization when the reaction
is performed from a chiral alkyl sulfonate or a sub-
strate having a C H acidic chiral center. The main
limitation of this procedure was found to be the con-
version of secondary alkyl sulfonates to alkyl chlor-
ides. In this case, the addition of a catalytic amount
of manganese chloride clearly accelerates the rate
and the efficiency of the reaction.
Keywords: alcohols; elimination; halides; manga-
nese; nucleophilic substitution; solvent effects

Introduction (Scheme 1).[2d] Consequently, the purification of the

Various procedures have been described for the con-
version of alkanols to alkyl halides.[1] A very classical
and soft method is to prepare the corresponding sul-
fonate and to treat it with a sodium or a lithium
halide.[1,2] This two-step preparation is very simple to
carry out and can generally be efficiently used with
sophisticated alcohols. Nevertheless, some limitations
remain since a polar solvent (acetone, DMF, DMSO)
is generally used to perform the SN2 substitution and
halide anions are then basic enough to give a competi-
tive elimination reaction (dehydrohalogenation). As
an example, the preparation of secondary alkyl hal-
ides according to the reaction conditions usually re-
ported often leads to moderate yields since variable
amounts of olefins are formed as side products
final secondary alkyl halide is tedious and it is very
often stained with variable amounts of olefins.
It should be noted that, by using a very polar sol-
vent such as HMPA, the elimination is frequently the
sole reaction.[3]
On the other hand, under the reaction conditions
generally used to perform the sulfonate/halide ex-
change, it is not possible to avoid the halide/halide ex-
change. Thus, enantiopure secondary alkyl sulfonates
generally give racemized secondary alkyl halides
(Scheme 2).[2c,4] This is mainly due to repeated SN2
substitutions.
In fact, all these drawbacks are favored by the use
of polar solvents. An alternative was proposed by
Gor in 1976.[5] He showed that the exchange can be
quickly performed under mild conditions in diethyl

Scheme 1.

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Scheme 2.
Scheme 3.
Scheme 4.
Scheme 5.
ether by using magnesium iodide or bromide
(Scheme 3).
The reaction works well with simple substrates
(Scheme 3), however, it is very sensitive to steric hin-
drance (Scheme 4).
It should be noted that the efficiency of magnesium
halides in ether is due to their complexation with sul-
fonates.[5] As a consequence, the reaction is clearly
less efficient with starting substrates bearing polar
functional groups (Scheme 5).
Moreover, magnesium iodide or bromide is gener-
ally used in a large excess (2 to 10 equiv.). Finally, it is
important to recall that the only way to obtain a solu-
tion of magnesium bromide or iodide in ether is to
prepare it directly in this solvent (Mg + I2 or Mg +
BrCH2CH2Br) since solid magnesium halides cannot
be dissolved in ether.
Recently, in the course of our studies on iron- and
cobalt-catalyzed cross-coupling reactions,[6] we were
interested in preparing various primary and secondary
Scheme 6.
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simple or functionalized alkyl bromides from the cor-
responding alcohols and we tried to improve the sul-
fonate-halogen exchange reaction described above.
Herein, we would like to report the results of our in-
vestigations in this field.
Results and Discussion
Various exchange reactions using lithium bromide
and alkyl mesylates in THF were reported but they
mainly involved reactive substrates such as allylic sul-
fonates.[1,7] On the other hand, only a few examples
are described with alkyl benzenesulfonates or alkyl
tosylates.[8] Moreover, to the best of our knowledge,
no general study on the scope and the advantages of
the use of lithium bromide has been published until
now. Herein, we highlight the usage of lithium bro-
mide or chloride in THF to limit the drawbacks dis-
cussed above.
Our first experiments (Table 1) have shown that, in
THF, various primary alkyl mesylates or benzenesul-
fonates smoothly react with lithium iodide, bromide
or chloride (entries 1 to 3) to give the corresponding
alkyl halides in excellent yields.
It should be noted that, in THF, the reaction is
often very slow at room temperature and it is necessa-
ry to work under reflux to accelerate the reaction. As
an example, the reaction of mesylate 1 with LiBr was
completed in 30 min at reflux (95% of 1-bromodode-
cane, entry 2) whereas at room temperature it re-
quires 2 days. Mesylates and benzenesulfonates lead
to similar yields, nevertheless, the exchange is gener-
ally faster from the later. Thus, dodecyl mesylate
1 reacts with LiCl in 24 h whereas the corresponding
benzenesulfonate 5 is completely converted in dode-
cyl chloride in only 5 h (entries 1 and 5). To the best
of our knowledge, such an observation was never re-
ported before.
Interestingly, in THF, the side formation of olefins
generally observed with secondary alkyl sulfonates
occurs to a significantly lower extent than with the
polar solvents generally employed until now. Thus, re-
action of 5-dodecyl tosylate 15 with LiBr in DMF
only gave 15% yield of 5 -bromododecane 16 whereas
90% were obtained in THF (Scheme 6).
Accordingly, various secondary alkyl bromides
were prepared efficiently in THF (Table 2). As a rule,
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Efficient Procedures to Prepare Primary and Secondary Alkyl Halides from Alkanols

Table 1. Preparation of primary alkyl, benzyl and allyl halides.

Entry Sulfonate LiX/reaction conditions Product Yield [%]

1 LiCl/reflux, 24 h 94

2 LiBr/reflux, 0.5 h 95

3 LiI/r.t., 12 h 99

4 LiBr/reflux, 0.5 h 98

5 LiCl/reflux, 5 h 96

6 LiBr/reflux, 12 h 82

7 LiCl/r.t., 6 h 83

8 LiBr/r.t., 2 h 89

9 LiCl/r.t., 6 h 97

10 LiCl/r.t., 12 h 77

alkyl benzenesulfonates or tosylates give higher yields

Table 2. Preparation of secondary alkyl bromides from the
corresponding sulfonates.
Entry Sulfonate Product Yield
[%]
1 90
2 80
4 75
5 89
6 75
7 65
than alkyl mesylates (entries 1 and 2).
A significant difference is also observed for the
preparation of primary alkyl halides from homoben-
zylic sulfonates that easily undergo a dehydrohaloge-
nation. For instance, the homobenzylic mesylate 26
afforded 72% of 2-phenylethyl bromide 27 and 17%
of styrene when the reaction was performed in DMF
whereas in THF the formation of styrene was not ob-
served and 27 was isolated in 94% yield (Scheme 7).
The reaction was successfully extended to various
base-sensitive sulfonates (Table 3).
Nucleophilic substitutions are more difficult in
THF than in the polar solvents generally used to
achieve a sulfonate/halide exchange reaction. Thus, in
THF it is possible to convert selectively the d-(+)-2-
octanol 36 to l-( )-2-bromooctane 37 via the corre-
sponding mesylate (Scheme 8) without racemization
due to repeated Br/Br exchanges (see Scheme 8).[9]
Unfortunately, when the chiral secondary alkyl bro-
mide is too reactive, for instance in the case of ethyl
2-bromopropionate 39, the racemization cannot be
avoided (Scheme 9).
It is interesting to note that the C H acidic stereo-
genic centers of the esters 41 and 43 are not race-
mized under the reaction conditions described above
(Scheme 10). As a comparison, in acetone, the conver-

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Scheme 7.
Table 3. Preparation of base-sensitive alkyl halides from the
corresponding sulfonates.
noted that this sulfonate/halide exchange quickly oc-
Entry Sulfonate LiX Product Yield
[%]
1 LiBr 94
2 LiI 85
3 LiBr 96
4 LiBr 95
5 LiBr 98
sion of the mesylate derived from alcohol 40 to bro-
mide 41 (LiBr, reflux, 12 h) occurs in a similar yield
but it is less stereoselective (only 75% ee) than in
THF.
As examplified above, the sulfonate/bromide ex-
change can be performed efficiently in THF. The re-
action has a very large scope and it is very efficient to
prepare primary and secondary alkyl bromides. En-
couraged by these results, we tried to prepare alkyl
chlorides by using LiCl. As expected, the advantage
of using THF instead of a more polar solvent like
DMF is even more important than with LiBr
(Scheme 11).
Unfortunately, the reaction is clearly slower, for in-
stance it lasts 72 h in the case of benzensulfonate 44.
In the course of our studies on organomanganese
chemistry,[10] we have observed that, during our at-
tempts to couple alkyl sulfonates with organomanga-
nese reagents RMnX·2 LiX (X = Br or Cl), alkyl
chlorides or bromides are frequently formed as side
products in substantial amounts. Moreover, we have
Scheme 8.
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Scheme 9.
curred, even in the case of the alkyl chlorides. There-
fore, we thought that it would be possible to acceler-
ate the sulfonate/chloride exchange by using the ate
complex MnCl2·2 LiCl instead of LiCl. Our first at-
tempt was successful since 6-tridecyl mesylate 18 is
converted to 6-tridecyl chloride 45 in 3 h instead of
72 h (Figure 1). Interestingly, it is possible to use only
a catalytic amount of manganese chloride. Thus, with
LiCl and 20% manganese chloride the reaction is
completed in only 8 h.
These results are very interesting from a preparative
point of view and the MnCl2-catalyzed procedure de-
scribed above was used to prepare various secondary
alkyl chlorides from the corresponding tosylates
(Table 4). The yields are satisfactory, even in the case
of base-sensitive alkyl sulfonates like 52 or 60.
The manganese catalysis is also efficient in diethyl
ether. Thus, dodecyl mesylate reacts slowly in diethyl
ether with lithium bromide to give only 60% yield of
dodecyl bromide whereas in the presence of manga-
nese bromide (20%) the reaction is faster and gave
90% yield (Figure 2).
The role of manganese chloride as a catalyst is not
clear. At first, it is important to note that, in the pres-
ence of LiX, manganese chloride is complexed to give
an ate complex MnCl2X2Li2.[10c,d,12] On the other hand,
it should be noted that lithium halogenometalates
have already be used as a soft halide ion source in or-
ganic synthesis. Thus, the opening of epoxides to halo-
hydrins was efficiently performed by using NiCl4Li2[13]
or CuCl4Li2.[14]
In our case, it is well known that SN2 substitution
reactions are more rapid when the degree of associa-
tion of the anion used as nucleophile with its counter-
ion is weak.[15] Moreover, the reaction is more effi-
cient when the nucleophile and the leaving group are
both soft or hard.[16] In the light of these considera-
tions, the role of manganese chloride would be to
form an ate complex in which the anionic part
MnCl42 is more free than the chloride anion issued
from LiCl. In THF, the dissociation of manganates
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Efficient Procedures to Prepare Primary and Secondary Alkyl Halides from Alkanols

Scheme 10.

Scheme 11.

Table 4. MnCl2-catalyzed preparation of secondary alkyl

chlorides from the corresponding sulfonates and LiCl.

Entry Sulfonate Product Yield [%]

1 83

2 81

3 75

4 85[a]
Figure 1. Influence of MnCl2 on the reaction of 6-tridecyl
mesylate with LiCl in THF.
5 60

into an anionic part MnCl42 and a solvated cation

[LiACHTUNGRE(thf)4]+ was already mentioned in the literature.[17] 6 74
In fact, the anion MnCl42 would act as an efficient
low basic chloride anion source. This was highlighted 7 99
in the case of the opening of epoxides since the elimi-
nation reactions due to the action of halide anions as
a base are completely ruled out by using lithium halo- 8 82
genometalates. In addition, an electrophilic activation
by the free [LiACHTUNGRE(thf)4]+ can also be considered as a co- 9 48
operative effect.
[a]
[a]: 37.1 (lit.[11] [a]: 37.3).
Conclusions
We have shown herein the potential of using lithium ondary alkyl sulfonates to alkyl halides in good to ex-
halides in THF to convert selectively primary and sec- cellent yields. The reaction has a large scope and can

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Figure 2. Influence of MnBr2 on the reaction of dodecyl me-
sylate with LiBr in ether.
be used successfully with base-sensitive alkyl sulfo-
nates or to convert stereospecifically secondary alka-
nols to the corresponding alkyl halides with an inver-
sion of configuration. The main limitation of this pro-
cedure is the conversion of secondary alkyl sulfonates
to alkyl chlorides that takes place very slowly. In this
case, we showed that the reaction is clearly accelerat-
ed in the presence of a catalytic amount of manganese
chloride.
Our goal was to study and to improve the halogen-
sulfonate exchange since this reaction is very often
the weak point of the well-known two-step procedure
for preparing an alkyl bromide or chloride from an al-
kanol via the corresponding alkyl sulfonate. Indeed, it
should be noted that the first step is never the limiting
step since alkyl sulfonates can generally be easily and
quantitatively prepared from alkanol then used in
crude form.[18] Therefore, the improvements reported
above increase the efficiency of the two step proce-
dure and extend its synthetic scope As exemplified in
Scheme 12, it is thus possible to prepare very effi-
ciently secondary alkyl chlorides from the corre-
sponding alcohols. This two-step procedure is very in-
teresting for preparative chemistry since all reagents
are very cheap and the reactions are very simple to
carry out.
Scheme 12.
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Experimental Section
Materials and Methods
1
H and 13C NMR spectra were recorded in ppm (d) at 400
and 100.5 MHz, respectively, with a JEOL ECX-400 NMR
spectrometer in CDCl3 as a solvent. Mass spectra were re-
corded on a Hewlett–Packard HP 5973 mass spectrometer
via a GC/MS coupling with a Hewlett–Packard HP 6890
chromatograph equipped with a capillary column HP-5MS
(50 m  0.25 mm  0.25 mm). Ionization was performed by
electronic impact (EI, 70 eV). High-resolution mass spectra
were obtained on a Jeol GCmate II. Ionization was obtained
by electronic impact (EI, 70 eV). Mass spectra are reported
as m/z.
Anhydrous THF (H2O < 5 ppm) was directly obtained
from commercial source and stored under a nitrogen atmos-
phere. Ether was distilled from sodium-benzophenone under
a nitrogen atmosphere. All other solvents (analytical grade)
were used without further purification. All reactions were
carried out under a nitrogen atmosphere under mechanical
stirring. Lithium chloride and bromide were purchased from
Acros and were dried for 8 h at 150 8C under vacuum.
Yields refer to isolated compounds. The purity was  96%
as determined by GC analysis (Hewlett Packard 6890 gas
chromatograph equipped with a HP-5 column). The analyti-
cal data for all compounds matches with the literature data.
Typical Procedure: Preparation of 2-Iodobenzyl
Mesylate (11)
2-iodobenzyl alcohol (4.68 g, 20 mmol) and dichloromethane
(100 mL) were introduced in a 500-mL flask under an argon
atmosphere. Triethylamine (3.03 g, 30 mmol) was added at
room temperature. Then, methanesulfonyl chloride (2.52 g,
22 mmol) was added at 10 8C. After 1.5 h at 10 8C, the re-
action was quenched with water (60 mL) and the organic
layer was washed quickly with a 1 N HCl solution (50 mL),
a saturated bicarbonate solution (50 mL) and brine (50 mL).
After drying over magnesium sulfate, filtration and evapora-
tion under vacuum, 2-iodobenzyl mesylate was obtained as
white-yellow crystals; yield: 97%. It is pure enough to be
used without further purification. 1H NMR (CDCl3): d =
8.03 (d, J = 8.1 Hz, 1 H), 7.65–7.48 (m, 2 H), 7.27–7.21 (m,
1 H), 5.42 (s, 2 H), 3.18 (s, 3 H); 13C NMR (CDCl3): d =
139.68, 135.85, 130.85, 130.33, 128.64, 98.56, 74.90, 38.06.
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Efficient Procedures to Prepare Primary and Secondary Alkyl Halides from Alkanols
Typical Procedure: Preparation of 6-Tridecyl
Benzenesulfonate (44)
6-Tridecanol (2 g, 10 mmol) and dichloromethane (10 mL)
were introduced in a 100 mL flask. Pyridine (1.58 g,
20 mmol) was added at room temperature then benzene sul-
fonyl chloride (2.65 g, 15 mmol) was added at 0 8C and the
reaction mixture was stirred at room temperature for 24 h.
The reaction mixture was quenched with water (20 mL) and
the organic layer was washed with HCl 1N solution (20 mL),
a sodium carbonate saturated solution (20 mL) and finally
with water (30 mL). After drying over magnesium sulfate,
filtration and evaporation in vacuo, the product was purified
by flash chromatography on a silica gel column (cyclohex-
ane/ethyl acetate 95:5). 3.17 g (93% yield) of 6-tridecylben-
zenesulfonate were obtained as a yellowish oil. 1H NMR
(CDCl3) d 8.04–8.00 (m, 2 H), 7.76–7.60 (m, 3 H), 4,72–4.63
(m, 1 H), 1,68–1.62 (m, 4 H), 1.37–1.27 (m, 16 H), 0.99–0.90
(m, 6 H); 13C NMR (CDCl3) d 137.61, 133.26, 128.91, 127.51,
84.85, 33.98, 31.56, 31.31, 29.09, 28.92, 24.57, 24.23, 22.48,
22.27, 13.95, 13.78.
General Procedure: Sulfonate-Halide Exchange
Reaction
THF or diethyl ether (15 mL), sulfonate (5 mmol) and lithi-
um halide (2 equiv., 10 mmol) were introduced in a 100-mL
flask under an argon atmosphere. Then, the reaction mix-
ture was refluxed for 0.5 h to 72 h (the reaction was moni-
tored by GC). The reaction times are indicated above. Then,
the reaction was quenched with water (20 mL) and the
product was extracted with diethyl ether (2  40 mL). After
drying over magnesium sulfate, filtration and evaporation
under vacuum, the product was purified by chromatography
on a silica gel column or by distillation.
General Procedure: Manganese-Catalyzed Sulfonate-
Halide Exchange Reaction
THF (15 mL), sulfonate (5 mmol) and lithium halide
(2 equiv., 10 mmol) were introduced in a 100-mL flask
under an argon atmosphere. Then, the reation mixture was
refluxed for 0.5 h to 24 h (the reaction was monitored by
GC). The reaction times are indicated above. Then, the re-
action was quenched with water (20 mL) and the product
was extracted with diethyl ether (2  40 mL). After drying
over magnesium sulfate, filtration and evaporation under
vacuum, the product was purified by chromatography on
a silica gel column or by distillation.
Chlorododecane (2): Colorless oil. It was prepared from
the corresponding mesylate or benzenesulfonate in THF.
The product was obtained in 94% yield. 1H NMR
(400 MHz, CDCl3): d = 3.53 (t, J = 6.8 Hz, 2 H), 1.91–1.68
(m, 2 H), 1.48–1.36 (m, 2 H), 1.35–1.10 (m, 16 H), 0.88 (t, J =
6.9 Hz, 3 H); 13C NMR (101 MHz, CDCl3): d = 45.22, 32.67,
31.92, 29.63 (2 C), 29.56, 29.48, 29.35, 28.91, 26.90, 22.70,
14.13; MS (EI, 70 eV): m/z = 204 (M+)
Bromododecane (3): Colorless oil. It was prepared from
the corresponding mesylate in THF. The product was ob-
tained in 95% yield. 1H NMR (400 MHz, CDCl3): d = 3.41
(t, J = 6.9 Hz, 2 H), 2.10–1.68 (m, 2 H), 1.52–1.37 (m, 2 H),
1.34–1.10 (m, 16 H), 0.88 (t, J = 6.9 Hz, 3 H); 13C NMR
(101 MHz, CDCl3): d = 34.10, 32.86, 31.93, 29.64 (2 C), 29.57,
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29.47, 29.37, 28.80, 28.21, 22.71, 14.15; MS (EI, 70 eV):
m/z = 249 (M+)
Iodododecane (4): Colorless oil. It was prepared from the
corresponding mesylate in THF. The product was obtained
in 99% yield. 1H NMR (400 MHz, CDCl3): d = 3.19 (t, J =
7.1 Hz, 2 H), 1.89–1.76 (m, 2 H), 1.43–1.17 (m, 18 H), 0.88 (t,
J = 6.9 Hz, 3 H); 13C NMR (101 MHz, CDCl3): d = 33.59,
31.93, 30.54, 29.64 (2 C), 29.58, 29.45, 29.37, 28.57, 22.71,
14.15, 7.42; MS (EI, 70 eV): m/z = 296 (M+)
1-Bromo-2-ethylhexane (7): Colorless oil. It was prepared
from the corresponding mesylate in THF. The product was
obtained in 82% yield. 1H NMR (400 MHz, CDCl3): d =
3.51–3.41 (m, 2 H), 1.57–1.48 (m, 1 H), 1.47–1.17 (m, 8 H),
0.84 (t, J = 7.3 Hz, 3 H), 0.82 (t, J = 7.3 Hz, 3 H); 13C NMR
(101 MHz, CDCl3): d = 41.04, 39.19, 31.88, 28.82, 25.16,
22.84, 14.06, 10.88; MS (EI): m/z = 193 (M+).
Benzyl Chloride (9): Colorless oil. It was prepared from
the corresponding mesylate in THF. The product was ob-
tained in 82% yield. 1H NMR (400 MHz, CDCl3): d = 7.43–
7.29 (m, 5 H), 4.59 (s, 2 H); 13C NMR (101 MHz, CDCl3):
d = 137.51, 128.78 (2 C), 128.62 (2 C), 128.44, 46.32; MS (EI):
m/z = 126 (M+).
Benzyl Bromide (10): Colorless oil. It was prepared from
the corresponding mesylate in THF. The product was ob-
tained in 89% yield. 1H NMR (400 MHz, CDCl3): d = 7.43–
7.26 (m, 5 H), 4.49 (s, 2 H); 13C NMR (101 MHz, CDCl3):
d = 137.82, 129.08 (2 C), 128.84 (2 C), 128.46, 33.63; MS (EI):
m/z = 171 (M+).
1-Chloromethyl-2-iodobenzene (12): It was prepared in
THF from the corresponding mesylate in 97% yield.
1
H NMR (400 MHz, CDCl3): d = 7.87 (dd, J = 7.9, 1.1 Hz,
1 H), 7.48 (dd, J = 7.7, 1.6 Hz, 1 H), 7.36 (td, J = 7.6, 1.2 Hz,
1 H), 7.01 (td, J = 7.7, 1.7 Hz, 1 H), 4.68 (s, 2 H); 13C NMR
(101 MHz, CDCl3): d = 139.89, 139.87, 130.26, 130.12, 128.80,
99.55, 51.07; MS (EI): m/z = 252 (M+).
Geranyl Chloride (14): It was prepared in THF from the
corresponding mesylate in 77% yield. 1H NMR (400 MHz,
CDCl3): d = 5.45 (ddd, J = 9.3, 6.8, 1.3 Hz, 1 H), 5.12–5.04
(m, 1 H), 4.11 (d, J = 8.0 Hz, 2 H), 2.15–2.02 (m, 4 H), 1.73
(d, J = 1.2 Hz, 3 H), 1.69 (d, J = 0.8 Hz, 3 H), 1.60 (s, 3 H);
13
C NMR (101 MHz, CDCl3) d 142.80, 132.00, 123.57,
120.25, 41.19, 39.45, 26.21, 25.68, 17.71, 16.12; MS (EI,
70 eV): m/z = 172 (M+)
6-Bromotridecane (16): Colorless oil. It was prepared in
THF from the corresponding tosylate or mesylate in, respec-
tively, 90 and 80% yield. The purification was performed by
distillation (bp 145 8C/2 mm Hg). 1H NMR (CDCl3): d =
4.18–4.08 (m, 1 H), 1.94–1.86 (m, 4 H), 1.69–1.31 (m, 16 H),
1.02–0.96 (m, 6 H); 13C NMR (CDCl3): d = 58.76, 39.19 (2C),
31.79, 31.39, 29.62, 29.33, 27.59, 27.24, 22.62, 22.52, 14.04
(2 C); MS (EI): m/z = 183 [CH3ACHTUNGRE(CH2)4CH+ACHTUNGRE(CH2)5CH3].
2-Bromooctane (19): Colorless oil. It was prepared in
THF from the corresponding tosylate in 75% yield. The pu-
rification was performed by distillation (bp 71 8C/
10 mm Hg). 1H NMR (400 MHz, CDCl3): d = 4.35–3.94 (m,
1 H), 1.90–1.64 (m, 5 H), 1.47–1.25 (m, 8 H), 0.88 (t, J =
7.0 Hz, 3 H); 13C NMR (101 MHz, CDCl3); d = 52.19, 41.40,
31.82, 28.80, 27.87, 26.60, 22.72, 14.20; MS (EI): m/z = 192
(M+).
5-Bromodecane (21): Colorless oil. It was prepared in
THF from the corresponding tosylate in 89% yield. The pu-
rification was performed by distillation (bp 54 8C/
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0.4 mm Hg). 1H NMR (400 MHz, CDCl3): d = 4.04 (ddd, J =
15.2, 7.7, 5.4 Hz, 1 H), 1.89–1.73 (m, 4 H), 1.64–1.22 (m,
10 H), 0.92 (t, J = 7.1 Hz, 3 H), 0.92–0.87 (t, J = 7.1 Hz, 3 H);
13
C NMR (101 MHz, CDCl3): d = 59.04, 39.14, 38.90, 31.26,
29.75, 27.26, 22.53, 22.18, 14.03, 13.99; MS (EI): m/z = 221
(M+).
Ethyl 5-bromododecanoate (23): Colorless oil. It was pre-
pared in THF from the corresponding benzenesulfonate in
75% yield. 1H NMR (400 MHz, CDCl3): d = 4.14 (q, J =
7.1 Hz, 2 H), 4.02 (ddd, J = 12.8, 7.5, 5.3 Hz, 1 H), 2.33 (dd,
J = 8.9, 5.3 Hz, 2 H), 1.96–1.69 (m, 6 H), 1.62–1.19 (m, 13 H),
0.88 (t, J = 6.9 Hz, 3 H); 13C NMR (101 MHz, CDCl3): d =
173.28, 60.37, 57.84, 39.11, 38.33, 33.59, 31.78, 29.14, 28.99,
27.54, 23.00, 22.63, 14.25, 14.09; MS (EI): m/z = 307 (M+);
HR-MS (EI, 70 eV): m/z = 306.1186; calcd. for (M+ 1):
306.1194.
1-Bromo-4-(3-bromobutyl)benzene (25): Colorless oil. It
was prepared in THF from the corresponding tosylate in
65% yield. 1H NMR (400 MHz, CDCl3): d = 7.41 (d, J =
8.4 Hz, 2 H), 7.08 (d, J = 8.4 Hz, 2 H), 4.04 (dqd, J = 9.1, 6.7,
4.3 Hz, 1 H), 2.76 (dddd, J = 16.1, 13.9, 8.7, 6.3 Hz, 2 H),
2.17–1.93 (m, 2 H), 1.72 (d, J = 6.7 Hz, 3 H); 13C NMR
(101 MHz, CDCl3): d = 139.83, 131.53 (2 C), 130.28 (2 C),
119.85, 50.52, 42.39, 33.36, 26.51; MS (EI): m/z = 292 (M+).
(2-Bromoethyl)benzene (27): Colorless oil. It was pre-
pared in THF from the corresponding mesylate in 94%
yield. 1H NMR (400 MHz, CDCl3): d = 7.58–6.86 (m, 5 H),
3.56 (dd, J = 10.1, 5.2 Hz, 2 H), 3.16 (dd, J = 9.8, 5.5 Hz, 2 H);
13
C NMR (101 MHz, CDCl3): d = 138.92, 128.69 (2 C),
128.65ACHTUNGRE(2 C), 126.96, 39.45, 32.98; MS (EI): m/z = 185 (M+).
1-Bromo-2-phenoxyethane (29): It was prepared in THF
from the corresponding benzenesulfonate in 94% yield.
1
H NMR (400 MHz, CDCl3): d = 7.34–7.26 (m, 2 H), 7.03–
6.95 (m, 1 H), 6.94–6.88 (m, 2 H), 4.29 (t, J = 6.3 Hz, 2 H),
3.64 (t, J = 6.3 Hz, 2 H); 13C NMR (101 MHz, CDCl3): d =
158.09, 129.63 (2 C), 121.47, 114.78 (2 C), 67.80, 29.19; MS
(EI): m/z = 201 (M+).
1-Iodo-2-phenoxyethane (30). It was prepared in THF
from the corresponding benzenesulfonate in 85% yield.
1
H NMR (400 MHz, CDCl3): d = 7.34–7.25 (m, 2 H), 7.03–
6.94 (m, 1 H), 6.94–6.86 (m, 2 H), 4.25 (t, J = 6.9 Hz, 2 H),
3.42 (t, J = 6.9 Hz, 2 H): 13C NMR (101 MHz, CDCl3): d =
158.05, 129.75 (2 C), 121.56, 114.95 (2 C), 68.71, 1.37; MS
(EI): m/z = 248 (M+).
(Z)-1-Bromo-3-nonene (32): Colorless oil. It was prepared
in THF from the corresponding mesylate in 96% yield.
1
H NMR (400 MHz, CDCl3): d = 5.47 (m, 1 H), 5.29 (m,
1 H), 3.30 (t, J = 7.2 Hz, 2 H), 2.68–2.47 (m, 2 H), 2.03–1.89
(m, 2 H), 1.35–1.15 (m, 6 H), 0.82 (t, J = 6.9 Hz, 3 H);
13
C NMR (101 MHz, CDCl3): d = 132.21, 124.69, 31.60,
30.44, 29.81, 28.16, 26.36, 21.52, 13.03; MS (EI): m/z = 205
(M+).
N-Benzyloxycarbonyl-2-bromoethylamine (35): It was
prepared in THF from the corresponding mesylate in 98%
yield. 1H NMR (400 MHz, CDCl3): d = 7.44–7.28 (m, 5 H),
5.19 (s, 1 H), 5.12 (s, 2 H), 3.61 (t, J = 5.8 Hz, 2 H), 3.48 (t,
J = 5.8 Hz, 2 H); 13C NMR (101 MHz, CDCl3): d = 156.17,
136.26, 128.59, 128.27, 128.16, 67.02, 44.07, 42.86, 42.78,
32.47; MS (EI): m/z = 258 (M+).
Methyl 2-(R)-bromopropanoate (39): Colorless oil. It was
prepared in THF from the corresponding alcohol via a mesy-
late in 74% yield. 1H NMR (400 MHz, CDCl3): d = 4.39 (q,
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J = 6.9 Hz, 1 H), 3.79 (s, 3 H), 1.84 (d, J = 6.9 Hz, 3 H);
13
C NMR (101 MHz, CDCl3): d = 170.76, 53.01, 39.77, 21.70;
[a]D : 17 (c 1, CH2Cl2) (Lit.[19] [a]D : 18); MS (EI): m/z =
167 (M+).
Methyl 3-bromo-2-(R)-methylpropanoate (41): Colorless
oil. It was prepared in THF from the corresponding alcohol
via a mesylate in 83% yield. 1H NMR (400 MHz, CDCl3):
d = 3.74 (s, 3 H), 3.64–3.43 (m, 2 H), 3.02–2.78 (m, 1 H), 1.30
(d, J = 7.0 Hz, 3 H); 13C NMR (101 MHz, CDCl3): d = 173.84,
52.13, 42.08, 34.08, 16.32; MS (EI): m/z = 181 (M+).
Benzyl 3-bromo-2-(N-tert-butoxycarbonylamino)propa-
noate (43): It was prepared in THF from the corresponding
alcohol via a mesylate in 97% yield. 1H NMR (400 MHz,
CDCl3): d = 7.48–7.31 (m, 5 H), 5.43 (d, J = 7.6 Hz, 1 H), 5.22
(q, J = 12.2 Hz, 2 H), 4.79 (dt, J = 6.9, 3.3 Hz, 1 H), 3.78 (ddd,
J = 52.2, 10.5, 3.3 Hz, 2 H), 1.45 (s, 9 H); 13C NMR
(101 MHz, CDCl3): d = 169.15, 154.98, 134.87, 128.65 (2 C),
128.46 (3 C), 80.53, 67.91, 53.97, 34.11, 28.26 (3 C). The enan-
tiomeric purity (95%) was determined, after reduction to al-
cohol with LiAlH4, then derivatization with the (S)-acetoxy-
propionyl chloride[20] , by 1H NMR and GC on a Lipodex-
E column (lengh: 50 m, internal diameter: 0.25 mm, film
width: 0.2 mm). This product was not suitable for GC/MS
(EI, 70 eV). HR-MS (EI, 70 eV): m/z = 357.0582; calcd. for
(M+): 357.0576.
6-Chlorotridecane (45): Colorless oil. It was prepared in
THF from the corresponding benzenesulfonate or mesylate
in, respectively, 83% and 81% yield. The purification was
performed by distillation (bp 124 8C/2 mm Hg). 1H NMR
(400 MHz, CDCl3): d = 3.95–3.83 (m, 1 H), 1.78–1.62 (m,
4 H), 1.59–1.46 (m, 2 H), 1.46–1.20 (m, 14 H), 0.88 (t, J =
6.6 Hz, 6 H); 13C NMR (101 MHz, CDCl3): d = 64.58, 38.67
(2 C), 31.87 (2 C), 29.01 (2 C), 26.62 (2 C), 22.75 (2 C), 14.23
(2 C); MS (EI): m/z = 183 [CH3ACHTUNGRE(CH2)4CH+ACHTUNGRE(CH2)5CH3].
2-Chlorotridecane (47): Colorless oil. It was prepared in
THF from the corresponding benzenesulfonate in 81%
yield. 1H NMR (400 MHz, CDCl3): d = 3.88–3.75 (m, 1 H),
1.86–1.58 (m, 4 H), 1.52–1.33 (m, 2 H), 1.33–1.18 (m, 14 H),
1.01 (t, J = 7.3 Hz, 3 H), 0.92–0.80 (m, 3 H); 13C NMR
(101 MHz, CDCl3): d = 66.06, 38.26, 32.07, 31.64, 29.76,
29.74, 29.68, 29.49, 29.36, 26.70, 22.84, 14.27, 11.10; MS (EI):
m/z = 220 (M+).
3-Chloropentane (49): Colorless oil. It was prepared in
THF from the corresponding benzenesulfonate in 75%
yield. After extractions using kerosene as the organic phase
(until no trace of THF is detected through GC analysis,
about 30 times), the purification was performed by distilla-
tion (bp 85 8C/760 mm Hg). 1H NMR (400 MHz, CDCl3): d =
3.79 (tt, J = 8.4, 4.5 Hz, 1 H), 1.84–1.65 (m, 4 H), 1.02 (t, J =
7.3 Hz, 6 H); 13C NMR (101 MHz, CDCl3): d = 67.63, 31.21
(2 C), 11.12 (2 C); MS (EI): m/z = 106 (M+).
(R)-2-Chlorooctane (51): Colorless oil. It was prepared in
THF from the corresponding benzenesulfonate in 85%
yield. 1H NMR (400 MHz, CDCl3): d = 4.04 (h, J = 6.5 Hz,
1 H), 1.79–1.62 (m, 2 H), 1.51 (d, J = 6.5 Hz, 3 H), 1.44–1.22
(m, 8 H), 0.96–0.86 (m, 3 H); 13C NMR (101 MHz, CDCl3):
d = 59.13, 40.55, 31.86, 28.95, 26.78, 25.51, 22.73, 14.21; MS
(EI): m/z = 113 [CH3CH+ACHTUNGRE(CH2)5CH3].
(2-Chloropropyl)benzene (53): Colorless oil. It was pre-
pared in THF from the corresponding benzenesulfonate in
60% yield. 1H NMR (400 MHz, CDCl3): d = 7.34–7.10 (m,
5 H), 4.19 (h, J = 6.7 Hz, 1 H), 3.05 (dd, J = 13.9, 7.0 Hz, 1 H),
Adv. Synth. Catal. 0000, 000, 0 – 0
Efficient Procedures to Prepare Primary and Secondary Alkyl Halides from Alkanols
2.93 (dd, J = 13.9, 6.9 Hz, 1 H), 1.51–1.40 (m, 3 H); 13C NMR
(101 MHz, CDCl3): d = 138.30, 129.67 (2 C), 128.74 (2 C),
127.12, 58.84, 47.02, 25.00; MS (EI): m/z = 154 (M+).
tert-Butyl 4-chloropiperidine-1-carboxylate (55): Colorless
oil. It was prepared in THF from the corresponding ben-
ACHTUNGREzenesulfonate in 74% yield after purification on silica gel
(eluting with petroleum ether/ethyl acetate = 98/2). 1H NMR
(400 MHz, CDCl3): d = 4.18 (tt, J = 7.6, 3.7 Hz, 1 H), 3.69
(ddd, J = 13.2, 7.2, 3.7 Hz, 2 H), 3.28 (ddd, J = 13.6, 7.7,
3.6 Hz, 2 H), 2.07–1.95 (m, 2 H), 1.79 (ddt, J = 15.7, 11.7,
5.6 Hz, 2 H), 1.45 (s, 9 H); 13C NMR (101 MHz, CDCl3): d =
154.75, 79.90, 57.06, 35.05 (2 C), 28.61 (2 C), 9.21 (3 C); MS
(EI): m/z = 219 (M+); HR-MS (EI, 70 eV): m/z = 219.1022,
calcd. for (M+): 219.1026.
5-Chlorododecanenitrile (57): Colorless oil. It was pre-
pared in THF from the corresponding benzenesulfonate in
99% yield after purification on silica gel (eluting with petro-
leum ether/ethyl acetate = 98/2). 1H NMR (400 MHz,
CDCl3): d = 3.96–3.83 (m, 1 H), 2.40 (t, J = 6.3 Hz, 2 H),
2.06–1.64 (m, 6 H), 1.60–1.18 (m, 10 H), 0.88 (h, J = 4.2 Hz,
3 H); 13C NMR (101 MHz, CDCl3): d = 119.44, 62.77, 38.71,
37.17, 31.88, 29.26, 29.18, 26.57, 22.76, 22.62, 16.94, 14.23;
MS (EI): m/z = 216 (M+). HR-MS (EI, 70 eV): m/z =
215.1437, calcd. for (M+): 215.1441.
Ethyl 5-chlorododecanoate (59): Colorless oil. It was pre-
pared in THF from the corresponding benzenesulfonate in
82% yield after purification on silica gel (eluting with petro-
leum ether/ethyl acetate = 98/2). 1H NMR (400 MHz,
CDCl3): d = 4.13 (q, J = 7.1 Hz, 2 H), 3.89 (dq, J = 5.4, 2.4 Hz,
1 H), 2.32 (t, J = 6.8 Hz, 2 H), 1.93–1.63 (m, 6 H), 1.57–1.35
(m, 2 H), 1.35–1.20 (m, 11 H), 0.91–0.84 (m, 3 H); 13C NMR
(101 MHz, CDCl3): d = 173.46, 63.72, 60.50, 38.59, 37.84,
33.85, 31.92, 29.31, 29.25, 26.60, 22.78, 22.07, 14.39, 14.24;
MS (EI): m/z = 263 (M+); HR-MS (EI, 70 eV): m/z =
262.1705, calcd. for (M+): 262.1700.
6-Chlorononan-2-one (61): Colorless oil. It was prepared
in THF from the corresponding benzenesulfonate in 48%
yield. 1H NMR (400 MHz, CDCl3): d = 3.97–3.84 (m, 1 H),
2.46 (td, J = 6.8, 1.7 Hz, 2 H), 2.14 (s, 3 H), 1.90–1.33 (m,
8 H), 0.92 (t, J = 7.4 Hz, 3 H); 13C NMR (101 MHz, CDCl3):
d = 208.62, 63.53, 43.14, 40.63, 37.87, 30.03, 20.87, 19.81,
13.70; MS (EI): m/z = 176 (M+). HR-MS (EI, 70 eV): m/z =
176.0966, calcd. for (M+): 176.0968.
Acknowledgements
We thank the CNRS and the University of Paris 13 for finan-
cial support.
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Efficient Procedures to Prepare Primary and Secondary 11

Alkyl Halides from Alkanols via the Corresponding
Sulfonates under Mild Conditions

Adv. Synth. Catal. 2012, 354, 1 – 11

Grard Cahiez,* Olivier Gager, Alban Moyeux,

Thomas Delacroix

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