Ligandless iron-catalyzed desulfinylative C-C allylation reactions using Grignard reagents and alk-2-enesulfonyl chlorides

Article abstract of DOI:10.1002/ejoc.200900927

Alk-2-enesulfonyl chlorides 1-4 were synthesized by the BCl3-promoted ene reaction of alkenes with SO2. These sulfonyl chlorides were then used as electrophilic partners in iron-catalyzed desulfinylative cross-coupling reactions with different Grignard reagents (aromatic, aliphatic, and heteroaromatic). The reaction can be catalyzed with even 2 mol-% of the simple iron salt Fe(acac)3. The regioselectivity of these allylations was studied by using sulfonyl chlorides 3 and 4 with aryl Grignard reagents. The scope of these allylations was further extended by the coupling of ester-substituted alk-2-enesulfonyl chloride 10 with aromatic Grignard reagents. Symmetrical products were synthesized by double C-C allylation with the use of 2-methylidenepropane-1,3-disulfonyl chloride (12). Wiley-VCH Verlag GmbH & Co. KGaA.

Full text of DOI:10.1002/ejoc.200900927

FULL PAPER
DOI: 10.1002/ejoc.200900927
Ligandless Iron-Catalyzed Desulfinylative C–C Allylation Reactions using
Grignard Reagents and Alk-2-enesulfonyl Chlorides
Chandra M. R. Volla,[a] Dean Markovic´,[a] Srinivas Reddy Dubbaka,[a] and Pierre Vogel*[a]
Keywords: Iron / Grignard reaction / Sulfur / Homogeneous catalysis / Cross-coupling
Alk-2-enesulfonyl chlorides 1–4 were synthesized by the
BCl3-promoted ene reaction of alkenes with SO2. These sul-
fonyl chlorides were then used as electrophilic partners in
iron-catalyzed desulfinylative cross-coupling reactions with
different Grignard reagents (aromatic, aliphatic, and
heteroaromatic). The reaction can be catalyzed with even
2 mol-% of the simple iron salt Fe(acac)3. The regioselectivity
of these allylations was studied by using sulfonyl chlorides 3
and 4 with aryl Grignard reagents. The scope of these al-
lylations was further extended by the coupling of ester-sub-
stituted alk-2-enesulfonyl chloride 10 with aromatic Grig-
nard reagents. Symmetrical products were synthesized by
double C–C allylation with the use of 2-methylidenepropane-
1,3-disulfonyl chloride (12).
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2009)
tion of Grignard reagents with alkane-, alkene-, and arene-
sulfonyl chlorides.[12] Here we demonstrate that sulfonyl
chlorides 1–4 can also be coupled with Grignard reagents
by using simple iron salts under ligandless conditions.
Introduction
Carbon–carbon cross-coupling reactions are very impor-
tant in the areas of material sciences and medicinal chemis-
try.[1] Transition-metal-catalyzed cross-coupling of organo-
metallic reagents (nucleophiles) with halides or triflates
(electrophiles) constitutes one of the most powerful meth-
ods to construct C–C bonds.[2] Arene- and alkanesulfonyl
chlorides are inexpensive and readily available compounds.
We have shown that Stille, carbonylative Stille,[3] Suzuki–
Miyaura,[4] Sonogashira–Hagihara,[5] Mizoroki–Heck,[6]
and Negishi[7] type cross-couplings can be carried out by
using sulfonyl chlorides as electrophilic partners under de-
sulfinylative conditions.[8] We have shown also that 2-meth-
ylprop-2-ene- (1), prop-2-ene- (2), 1-methylprop-2-ene- (3),
and (E)-but-2-enesulfonyl chloride (4) are useful electro-
philic partners in desulfinylative palladium-catalyzed C–C
coupling reactions with inexpensive Grignard reagents and
sodium salts of malonic esters and methyl acetoacetate.[9]
As these sulfonyl chlorides can now be prepared in one-pot
operations (Scheme 1) through a BCl3-promoted ene reac-
tion of the corresponding simple monoalkenes with sulfur
dioxide,[10] substrates 1–4 have become now powerful elec-
trophilic allylating agents (without BCl3, the ene reaction
of simple monoalkenes with SO2 is endergonic above
–100 °C).[11] Previously, we have shown that iron catalysts
can be used in the desulfinylative C–C cross-coupling reac-
Scheme 1. One-pot synthesis of alk-2-enesulfonyl chlorides.[27]
Results and Discussion
In 1954, Kharasch and Reinmuth,[13] and in 1971, Ta-
mura and Kochi,[14] proposed to use of iron catalysts for
the C–C cross-coupling reactions of Grignard reagents with
alkyl halides. In the meantime, iron catalysts have become
very popular for related reactions.[15–25] Recently, Sonoga-
shira–Hagihara,[26,27] Mizoroki–Heck[28] and Suzuki–Mi-
yaura C–C cross-coupling reactions[29] have been catalyzed
by iron salts or iron complexes.
Screening of the iron catalysts was carried out by using
o-tolylmagnesium chloride (5a) and 2-methylprop-2-enesul-
fonyl chloride (1) at room temperature. Our results are sum-
marized in Table 1. As for the desulfinylative C–C cross-
coupling reactions of alkane- and alkenylsulfonyl chlorides
[a] Laboratory of Glycochemistry and Asymmetric Synthesis
(LGSA), Swiss Federal Institute of Technology-Lausanne
(EPFL), Batochime,
1015, Lausanne, Switzerland
Fax: +41-21-693-9375
E-mail: pierre.vogel@epfl.ch
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.200900927.
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C. M. R. Volla, D. Markovic´, S. R. Dubbaka, P. Vogel
FULL PAPER
with Grignard reagents,[12] air-stable Fe(acac)3 in THF ap- Table 2. Iron-catalyzed allylation of Grignard reagents with allyl-
sulfonyl chlorides.
pears to be a better catalyst than FeCl3 or FeF3 (Table 1,
Entry 1 vs. 7). The use of a cosolvent like NMP (N-methyl-
pyrrolidone) did not improve the reaction (Table 1, En-
try 3). Contrary to aliphatic sulfonyl chlorides, which re-
quire refluxing temperatures for the successful reaction,
these allylations occur smoothly at room temperature with
good yields. Interestingly, the reaction can be run with only
2 mol-% of Fe(acac)3 in THF, although it takes longer time
for completion.
Table 1. Screening of iron salts for the coupling of 2-methylprop-
2-enesulfonyl chloride (1) with o-tolylmagnesium chloride (5a).[a]
Entry
Fe catalyst
Solvent
Time [h] Yield[b] [%]
1
2
3
4
5
6
7
Fe(acac)3
Fe(acac)3
THF
DME
3
2
2
2
8
3
4
82
75
Fe(acac)3 THF/NMP (4:1)[c]
78
Fe(acac)3
Fe(acac)3
FeCl3
THF
THF
THF
THF
73[d]
61[e]
78
FeF3
58
[a] Sulfonyl chloride (1.0 equiv.) with the Grignard reagent
(1.5 equiv.) in the presence of the iron salt (5 mol-%) in the given
solvent (5 mL). [b] Yield of isolated product after column
chromatography on silica gel. [c] A mixture of THF (4 mL) and
NMP (1 mL) was used as solvent. [d] Reaction was done under
reflux instead of at room temperature. [e] Reaction was done with
2 mol-% of Fe(acac)3. THF = tetrahydrofuran, DME = dimethoxy-
ethane, NMP = N-methylpyrrolidone.
Even more interestingly, for reactions done at room tem-
perature no sulfone was formed. This is not the case with
non-allylic sulfonyl chlorides. This suggests that the low-
[a] Yield of isolated product after flash column chromatography on
silica gel.
valent iron species generated upon reaction of the Grignard
[25,30,31]
reagent with Fe(acac)3
coordinates to the alkene
quickly, which accelerates the oxidative addition on the C–
S bond, leading to an allyliron-type of intermediate.
ethane (DME) and acetonitrile the ratio was slightly better
We then explored the scope of this new iron-catalyzed (9:1 and 88:12, respectively). Using iron salts other than
electrophilic allylation by using sulfonyl chlorides 1 and 2 Fe(acac)3 such as FeCl3 in THF or FeBr3 in THF led to
with various aryl and alkyl Grignard reagents. Good yields the best regioselectivity (9:1). FeCl3/DME was not as good
for products 6 and 7 were obtained in most cases, as shown as FeCl3/THF. No improvement could be observed with
in Table 2. Differently substituted aromatic Grignard rea- FeCl2 (Table 3, Entry 8), Fe(ClO4)2 (Table 3, Entry 9),
gents and a heteroaromatic Grignard reagent coupled nicely FeBr2 (Table 3, Entry 12), and FeF3 (Table 3, Entry 10) in
under the optimized conditions with alk-2-enesulfonyl chlo- THF, but interestingly, all these iron salts did catalyze the
rides. The successful application of aliphatic Grignard rea- desulfinylative C–C cross-coupling reaction requiring some-
gents as the coupling partners will increase the scope of what longer reactions times than with Fe(acac)3. With
these iron-catalyzed coupling reactions (Table 2, Entries 7, Fe2O3 in THF (Table 3, Entry 13) only trace amounts of
8, and 11).
product 10a + 11a were formed, probably because of the
Using o-tolylmagnesium chloride (5a), we examined the low solubility of iron oxide.
regioselectivity of its cross-coupling with a 3:1 mixture of
We explored the scope of the allylation reaction with 3
(E)- and (Z)-but-2-enesulfonyl chloride (3; Table 3). Apply- for p-tolylmagnesium bromide (5b) and p-methoxyphen-
ing our standard conditions [5 mol-% of Fe(acac)3, THF, ylmagnesium bromide (5c) by using Fe(acac)3 (5 mol-%) as
r.t.], the product ratio was found to be 86:14 (8a vs. 9a). catalyst in DME at 25 °C. After 4 h, 88:12 and 85:15 mix-
Changing solvent from THF to toluene did not improve tures of products 8b/9b and 8c/9c were obtained in 82 and
this regioselectivity (Table 3, Entry 2). In 1,2-dimethoxy- 85% yield, respectively (Table 4). Interestingly, nearly the
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Eur. J. Org. Chem. 2009, 6281–6288

Ligandless Iron-Catalyzed Desulfinylative C–C Allylation Reactions
Table 3. Regioselectivity of the allylation of o-tolylmagnesium chlo-
ride (5a) with a 3:1 mixture of (E)- and (Z)-but-2-enesulfonyl chlo-
ride (3).
Entry
Fe catalyst
Solvent
Ratio[a] (% yield)[b]
1
2
3
4
5
6
7
8
Fe(acac)3
Fe(acac)3
Fe(acac)3
Fe(acac)3
Fe(OAc)2
FeCl3
THF
toluene
DME
CH3CN
THF
THF
DME
THF
86:14 (78)
85:15
90:10 (75)
88:12 (57)
85:15
90:10 (68)
84:16 (71)
87:13
Scheme 2. Iron-catalyzed coupling of a functionalized alk-2-ene-1-
sulfonyl chloride with Grignard reagents.
FeCl3
FeCl2
The scope of the iron-catalyzed cross-coupling reaction
was further tested by using disulfonyl dichloride 12. It re-
acted with different aromatic Grignard reagents under our
standard conditions with the use of Fe(acac)3 (5 mol-%).
The reactions were completed in 6 h to give the symmetri-
cally substituted coupling products 13 in good yields
(Scheme 3).
9
Fe(ClO4)2
FeF3
FeBr3
FeBr2
Fe2O3
THF
THF
THF
THF
83:17
80:20
90:10
85:15
10
11
12
13
THF
traces
[a] The 8/9 product ratio was determined by analysis of the 1H
NMR spectrum of the crude reaction mixture. [b] Yield of 8 + 9
determined after column chromatography on silica gel.
same mixtures of 8a/9a, 8b/9b, and 8c/9c were obtained
when using 2-methylprop-2-enesulfonyl chloride (4) as elec-
trophilic allylating agent (Table 4) in comparable yields.
Scheme 3. Coupling of disulfonyl dichlorides with Grignard rea-
gents.
Table 4. Scope of the iron-catalyzed coupling of sulfonyl chlorides
with Grignard reagents.
The same regioselectivity was obtained starting either
with sulfonyl chloride 3 or 4. This suggests that the same
type of 1-methylallyl iron intermediate was formed indepen-
dently from 3 and 4 and that they coupled with the Grig-
nard reagents with nearly the same regioselectivity, indepen-
dent of the nature of the initial iron salt and the nature of
the arylmagnesium reagent. The preference for non-
branched products 8 can be attributed to a steric effect that
renders the insertion of the aryl group easier at the unsub-
Entry RSO2Cl
RЈ
Yield[a]
[%]
Ratio
Ratio
(E)-8/(Z)-8
(product)[b]
1
2
3
4
5
6
3
3
3
4
4
4
o-tolyl (5a)
p-tolyl (5b)
p-methoxyphenyl (5c)
o-tolyl (5a)
p-tolyl (5b)
p-methoxyphenyl (5c)
75
82
85
72
77
79
90:10 (8a+9a)
88:12 (8b+9b)
85:15 (8c+9c)
88:12 (8a+9a)
87:13 (8b+9b)
84:16 (8c+9c)
10: 1
6:1
8:1
10:1
6:1
8:1
[a] Yield of 8a + 9a determined after column chromatography on
silica gel. [b] The 8/9 product ratio was determined by analysis of
1
the H NMR spectrum of the crude reaction mixture.
We have already demonstrated that coupling of sulfonyl
chlorides with Grignard reagents tolerates a wide range of
functional groups, including carbonyl groups which are
prone to react with Grignard reagents. To further expand
the scope of these coupling reactions, we prepared allyl sul-
fonyl chloride 10 containing an allyl ester group
(Scheme 2).[32] As proof of principle, 10 was treated with
Grignard reagents and to our delight the coupling reaction
tolerated the ester functional group to give the correspond-
ing products 11. This reaction shows that (a) ester groups
are tolerated in the coupling reaction and (b) alk-2-enesul-
fonyl chloride was more reactive than allyl ester towards the
Grignard reagent.
Scheme 4. Proposed mechanism for the iron-catalyzed desulfin-
ylative allylation of Grignard reagents with alk-2-enesulfonyl chlo-
rides.
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C. M. R. Volla, D. Markovic´, S. R. Dubbaka, P. Vogel
FULL PAPER
of SO2 and the solvent were evaporated under reduced pressure
(10–3 Torr) to dryness (ca. 1 h). NCS (5.7 g, 42.8 mmol, 1.2 equiv.)
dissolved in DCM was added to the reaction mixture at –20 °C,
and the mixture was allowed to reach room temperature in 3 h.
The reaction mixture was quenched with water, and the aqueous
layer was extracted with DCM (3ϫ100 mL). The combined or-
ganic phase was dried (MgSO4), filtered, and concentrated under
reduced pressure. The crude mixture was filtered through a pad of
silica gel to obtain 1 (4.67 g, 30.3 mmol, 85%) as a colorless oil.
1H NMR (400 MHz, CDCl3): δ = 2.01 (s, 3 H, Me), 4.34 (s, 2 H,
stituted end of the allyl moiety than at the substituted end.
The mechanism shown in Scheme 4 interprets the data pre-
sented.
Conclusion
In conclusion, we have developed a new iron-catalyzed
desulfinylative coupling of alk-2-enesulfonyl chlorides
(which can be prepared easily from alkenes) with Grignard
reagents in THF. A variety of nucleophilic reagents like aro-
matic, aliphatic, and heteroaromatic Grignard reagents
CH2), 5.32 (br. s, 1 H, olefinic), 5.41 (br. s, 1 H, olefinic) ppm. 13
C
NMR (100.6 MHz, CDCl3): δ = 22.2, 73.2, 124.2, 132.0 ppm. MS
(CI, NH3): m/z (%) = 172 (4) [M + 18]+, 154 (1) [M + 1]+, 90 (10)
were coupled with alk-2-enesulfonyl chlorides under mild [M – 64]+, 72 (100) [M – 82]+.
conditions (room temperature, no ligand, harmless solvent)
to give the C–C cross-coupling products in high yields. Al-
lylations with the use of but-2-ene-1-sulfonyl and but-3-ene-
2-sulfonyl chloride and aryl Grignard reagents led to the
same mixture of regioisomers (85:15 to 9:1), favoring linear
products. Preliminary experiments showed that our C–C
cross-coupling conditions are tolerant towards allylic ester
moieties (Scheme 2). Symmetrical products resulting from
Prop-2-ene-1-sulfonyl Chloride (2):[34] Using the same procedure as
that used for 1, starting from 1-propene (2.0 g, 47.6 mmol, 1 equiv.)
in the presence of a solution of BCl3 (1.0  in DCM, 47.6 mL),
product 2 (5.4 g, 38.6 mmol, 81%) was obtained as a colorless oil.
1H NMR (400 MHz, CDCl3): δ = 4.34 (d, J = 7.4 Hz, 2 H, CH2),
5.71 (m, 2 H, olefinic), 6.05 (m, 1 H, olefinic) ppm. 13C NMR
(100.6 MHz, CDCl3): δ = 69.0, 123.4, 128.1 ppm. MS (CI, NH3):
m/z (%) = 158 (16) [M + 18]+, 140 (22) [M]+, 76 (100) [M – 64]+.
the double C–C coupling of 2-methylidenepropane-1,3-dis- 2-Butene-1-sulfonyl Chloride (3):[35] Using the same procedure as
that used for 1, starting from 1-butene (2.0 g, 35.7 mmol, 1 equiv.)
in the presence of a solution of BCl3 (1.0  in DCM, 36 mL), prod-
uct 3 (4.78 g, 31.0 mmol, 87%) was obtained as a light yellow oil.
1H NMR (400 MHz, CDCl3): δ = 1.72 (d, J = 6.8 Hz, 3 H, Me),
4.26 (m, 1 H, CH), 5.62 (m, 1 H, olefinic), 5.98 (m, 1 H, olefinic)
ppm. 13C NMR (100.6 MHz, CDCl3): δ = 18.4, 77.5, 127.9,
132.5 ppm. MS (CI, NH3): m/z (%) = 154 (27) [M]+, 98 (100)
[M – 55]+.
ulfonyl dichloride were also obtained in good yields. This
new chemistry takes special value knowing that alk-2-enes-
ulfonyl chlorides can be prepared by the BCl3-promoted ene
reaction of alkenes with SO2 (Scheme 1).
Experimental Section
Methods: Unless stated otherwise, reactions were conducted in
flame-dried glassware under a vacuum. THF was distilled before
use from sodium and benzophenone. Solvents after reactions and
extraction were evaporated in a rotary evaporator under vacuum
(solvents were removed by cooling at –20 °C for low-boiling or low-
molecular-mass compounds). TLC for reaction monitoring was
performed on 60 F254 (Merck) with detection by UV light and char-
3-Butene-2-sulfonyl Chloride (4):[9] Using the same procedure as
that for 1, starting from 2-butene (2.0 g, 35.7 mmol, 1 equiv.) in the
presence of a solution of BCl3 (1.0  in DCM, 36 mL), product 4
(4.34 g, 28.2 mmol, 79%) was obtained as a light yellow oil. 1H
NMR (400 MHz, CDCl3): δ = 1.65 (d, J = 6.5 Hz, 3 H, Me), 3.54
(d, J = 7.4 Hz, 2 H, CH2), 5.52 (m, 1 H, olefinic), 5.81 (m, 1 H,
olefinic) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 18.6, 68.9,
116.0, 140.6 ppm. MS (CI, NH3): m/z (%) = 155 (47) [M + 1]+, 88
(100) [M – 66]+.
1
ring with KMnO4 or Pancaldi reagent. H and 13C NMR spectra
were recorded with Bruker-DPX-400 or Bruker-ARX-400 spec-
trometer at 400 MHz and 100.6 MHz, respectively, and are re-
ported relative to Me4Si (δ = 0.0 ppm) or to the solvents residual
2-[(Chlorosulfonyl)methyl]allyl Acetate (10): TMSOTf (2.16 mmol,
20 mol-%) in anhydrous CH3CN (10 mL) was degassed by freeze–
thaw cycles on the vacuum line. Sulfur dioxide (0.21 mol,
20 equiv.), dried through a column packed with phosphorus pent-
oxide and aluminum oxide, was transferred on the vacuum line to
the CH3CN solution frozen at –196 °C. The mixture was allowed
to melt and to warm to –40 °C. After 30 min at this temperature, 2-
(trimethylsilylmethyl)allyl acetate (10.8 mmol, 1 equiv.) was added
slowly. The mixture was stirred at –20 °C for 12 h. After cooling to
–78 °C, the excess amount of SO2 and the solvent were evaporated
under reduced pressure (10–3 Torr) to dryness (ca. 1 h). Halogenat-
ing agent (NCS 16.2 mmol, 1.2 equiv., dissolving in CH3CN) was
1
1H signal (CHCl3, δH = 7.27 ppm). Data for H NMR spectra are
reported as follows: chemical shift, multiplicity, coupling constant,
and integration. Data for 13C NMR spectra reported in terms of
chemical shift. IR spectra were recorded with a Perkin–Elmer-1420
spectrometer and are reported in frequency of absorption (cm–1).
High-resolution MALDI-TOF mass spectra were obtained from
the Institute of Molecular and Biology Chemistry, Swiss Institute
of Technology Mass Spectral Facility, EPFL, Lausanne. 1,3-
Bischlorsulfonyl-2-methylenepropane was prepared from a known
procedure.
2-Methylprop-2-ene-1-sulfonyl Chloride (1):[33] In a two-necked, added to the reaction mixture at –20 °C. After 3 h at this tempera-
100–mL, round-bottomed flask was placed a solution of BCl3
(1.0  in DCM, 36 mL, 35.7 mmol, 1 equiv.) under an argon atmo-
sphere. Sulfur dioxide (0.71 mol, 20 equiv.), dried through a column
packed with phosphorus pentoxide and aluminum oxide, was trans-
ferred on the vacuum line to the solution frozen at –196 °C. The
ture, the reaction mixture was quenched with water, and the aque-
ous layer was extracted with DCM (3ϫ100 mL). The combined
organic phase was dried (MgSO4), filtered, and concentrated under
reduced pressure. The crude mixture was purified by column
chromatography on silica gel (petroleum ether/ether, 9:1) to obtain
mixture was allowed to melt and to warm to –40 °C. After 30 min 10 (1.49 g, 7.0 mmol, 65%) as a light yellow oil. IR (film): ν =
˜
at this temperature, 2-methylpropene (2.0 g, 35.7 mmol, 1 equiv.)
was transferred to the solution frozen at –196 °C. The mixture was
stirred at –20 °C for 6 h. After cooling to –78 °C, the excess amount
2922, 1736, 1369, 1223, 1168, 1035, 941, 677, 632, 602 cm–1. 1H
NMR (400 MHz, CDCl3): δ = 2.10 (s, 3 H, Me), 4.44 (s, 2 H, CH2),
4.76 (s, 2 H, OCH2), 5.66 (s, 1 H, olefinic), 5.75 (s, 1 H, olefinic)
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Ligandless Iron-Catalyzed Desulfinylative C–C Allylation Reactions
ppm. 13C NMR (100.6 MHz, CDCl3): δ = 20.7, 65.1, 68.3, 126.7, 8.0 Hz), 135.3 (d, J = 2.9 Hz), 145.1, 161.4 (d, J = 244.2 Hz) ppm.
131.2, 170.2 ppm. HRMS (ESI-TOF): calcd. for C6H9ClO4S MS (CI, NH3): m/z (%) = 151 (7) [M + 1]+, 150 (61) [M]+, 135
212.9988; found 212.9985.
(100) [M – 15]+, 115 (20) [M – 35]+, 109 (60) [M – 41]+.
N,N-Dimethyl-4-(2-methylallyl)benzenamine (Table 2, Entry 5):[38]
Following the typical experimental procedure, sulfonyl chloride 1
(0.1 g, 0.65 mmol, 1 equiv.) and 4-(N,N-dimethyl)aniline magne-
sium bromide (5e; 0.5  in THF, 2.0 mL, 1.0 mmol, 1.5 equiv.) gave
the product (86 mg, 76%) as a dark brown oil. 1H NMR
(400 MHz, CDCl3): δ = 1.71 (s, 3 H, Me), 2.95 [s, 6 H, N(CH3)2],
3.26 (s, 2 H, CH2), 4.75 (s, 1 H, olefinic), 4.81 (s, 1 H, olefinic),
6.73 (d, J = 8.8 Hz, 2 H, arom.), 7.09 (d, J = 8.8 Hz, 2 H, arom.)
ppm. 13C NMR (100.6 MHz, CDCl3): δ = 22.1, 40.9, 43.7, 111.2,
112.9, 127.9, 129.5, 146.0, 149.2 ppm. HRMS (ESI-TOF): calcd.
for C12H17N 176.1439; found 176.1440.
Typical Experimental Procedure for the Iron-Catalyzed Desul-
finylative Allylations: In a glove box under a nitrogen atmosphere,
a round-bottomed flask, dried under vacuum, was charged with
the corresponding sulfonyl chloride (1 equiv.) and Fe(acac)3
(5 mol-%). Then, the flask was connected to a vacuum line and
filled with argon (3ϫ) and solvent (5 mL). The corresponding Grig-
nard reagent (1.5 equiv.) was added dropwise over 5–10 min by sy-
ringe. The reaction mixture was stirred until complete disappear-
ance of the starting material. The mixture was quenched with a
saturated aqueous solution of NH4Cl (10 mL) and diluted with di-
ethyl ether. The aqueous layer was extracted again with diethyl
ether (3ϫ20 mL). The combined organic phase was dried
(MgSO4), filtered, and concentrated under reduced pressure. The
residue was purified by flash chromatography on silica gel eluting
with pentane.
2-(2-Methylallyl)thiophene (Table 2, Entry 6): Following the typical
experimental procedure, sulfonyl chloride 1 (0.1 g, 0.65 mmol,
1 equiv.) and thiophen-2-yl-magnesium bromide (5f; 1.0  in THF,
1.0 mL, 1.0 mmol, 1.5 equiv.) gave the product (57 mg, 64%) as a
1-Methyl-2-(2-methylallyl)benzene (Table 2, Entry 1):[7] Following
the typical experimental procedure, sulfonyl chloride 1 (0.1 g,
0.65 mmol, 1 equiv.) and o-tolylmagnesium chloride (5a; 1.0  in
THF, 1.0 mL, 1.0 mmol, 1.5 equiv.) gave the product (78 mg 82%)
colorless oil. IR (film): ν = 2977, 1383, 1111, 904, 727, 650, 632,
˜
544, 532 cm–1. 1H NMR (400 MHz, CDCl3): δ = 1.77 (s, 3 H, Me),
3.54 (s, 2 H, CH2), 4.86 (br. s, 2 H, olefinic), 6.83–6.86 (m, 1 H,
arom.), 6.96 (dd, J = 5.1, 3.3 Hz, 1 H, arom.), 7.17 (dd, J = 5.1,
1.2 Hz, 1 H, arom.) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 21.8,
38.5, 112.1, 123.7, 125.3, 126.7, 142.6, 144.5 ppm. MS (CI, NH3):
m/z (%) = 139 (11) [M + 1]+, 138 (98) [M]+, 123 (100) [M – 15], 97
(93) [M – 41]+. HRMS (ESI-TOF): calcd. for C8H10S 139.0581;
found 139.0583.
1
as a light yellow oil. H NMR (400 MHz, CDCl3): δ = 1.77 (s, 3
H, Me), 2.31 (s, 3 H, Me-arom.), 3.35 (s, 2 H, CH2), 4.56 (s, 1 H,
olefinic), 4.84 (s, 1 H, olefinic), 7.15–7.19 (m, 4 H, arom.) ppm.
13C NMR (100.6 MHz, CDCl3): δ = 19.3, 22.7, 41.8, 111.5, 125.8,
126.3, 129.8, 130.1, 136.8, 137.9, 144.2 ppm. MS (CI, NH3): m/z
(%) = 147 (8) [M + 1]+, 146 (68) [M]+, 131 (100) [M – 15], 105 (19)
[M – 41]+, 91 (33) [M – 55]+.
1-Methyl-4-(2-methylallyl)benzene (Table 2, Entry 2):[36] Following
the typical experimental procedure, sulfonyl chloride 1 (0.1 g,
0.65 mmol, 1 equiv.) and p-tolylmagnesium bromide (5b; 1.0  in
THF, 1.0 mL, 1.0 mmol, 1.5 equiv.) gave the product (75 mg, 79%)
as an oil. 1H NMR (400 MHz, CDCl3): δ = 1.72 (s, 3 H, Me), 2.40
(s, 3 H, Me-arom.), 3.32 (s, 2 H, CH2), 4.47 (s, 1 H, olefinic), 4.83
(s, 1 H, olefinic), 7.12–7.15 (m, 4 H, arom.) ppm. 13C NMR
(100.6 MHz, CDCl3): δ = 21.0, 22.1, 44.2, 111.7, 128.8, 129.0,135.5,
136.7, 145.4 ppm. MS (CI, NH3): m/z (%) = 147 (7) [M + 1]+, 146
(63) [M]+, 131 (100) [M – 15], 105 (29) [M – 41]+, 91 (43)
[M – 55]+.
(2-Methylallyl)cyclohexane (Table 2, Entry 7):[39] Following the typ-
ical experimental procedure, sulfonyl chloride 1 (0.1 g, 0.65 mmol,
1 equiv.) and cyclohexylmagnesium chloride (5g; 2.0  in Et2O,
0.5 mL, 1.0 mmol, 1.5 equiv.), gave the product (55 mg, 61%) as a
colorless oil. 1H NMR (400 MHz, CDCl3): δ = 0. 84 (m, 2 H,
cyclohexyl), 1.21–1.50 (m, 8 H, cyclohexyl), 1.52 (m, 1 H, cyclo-
hexyl), 1.71 (s, 3 H, Me), 1.91 (d, J = 7.3 Hz, 2 H, CH2), 4.65 (br.
s, 1 H, olefinic), 4.74 (br. s, 1 H, olefinic) ppm. 13C NMR
(100.6 MHz, CDCl3): δ = 22.3, 26.4, 26.6, 33.3, 35.4, 46.2, 111.1,
144.6 ppm. MS (CI, NH3): m/z (%) = 138 (7) [M]+, 123 (2)
[M – 15]+, 82 (49) [M – 56]+, 67 (49) [M – 71]+, 55 (100)
[M – 83]+.
(4-Methylpent-4-enyl)benzene (Table 2, Entry 8):[40] Following the
1-Methoxy-4-(2-methylallyl)benzene (Table 2, Entry 3):[37] Follow-
ing the typical experimental procedure, sulfonyl chloride 1 (0.1 g,
0.65 mmol, 1 equiv.) and 4-methoxyphenylmagnesium bromide (5c;
0.5  in THF, 2.0 mL, 1.0 mmol, 1.5 equiv.) gave the product
(91 mg, 87%) as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ
= 1.71 (s, 3 H, Me), 3.31 (s, 2 H, CH2), 3.85 (s, 3 H, OMe), 4.76
(s, 1 H, olefinic), 4.83 (s, 1 H, olefinic), 6.88 (d, J = 8.7 Hz, 2 H,
arom.), 7.15 (d, J = 8.7 Hz, 2 H, arom.) ppm. 13C NMR
(100.6 MHz, CDCl3): δ = 22.0, 43.7, 55.3, 111.5, 113.7, 129.8,
131.9, 145.6, 158.0 ppm. MS (CI, NH3): m/z (%) = 163 (13)
[M + 1]+, 162 (98) [M]+, 147 (100) [M – 15], 121 (70) [M – 41]+,
91 (29) [M – 71]+.
typical experimental procedure, sulfonyl chloride
1 (0.1 g,
0.65 mmol, 1 equiv.) and 2-phenethylmagnesium chloride (5h; 1.0 
in THF, 1.0 mL, 1.0 mmol, 1.5 equiv.) gave the product (58 mg,
1
56%) as a light yellow oil. H NMR (400 MHz, CDCl3): δ = 1.74
(s, 3 H, Me), 1.75–1.82 (m, 2 H, CH2), 2.07 (t, J = 7.5 Hz, 2 H,
CH2), 2.62 (t, J = 7.8 Hz, 2 H, CH2), 4.71 (br. s, 1 H, olefinic),
4.74 (br. s, 1 H, olefinic), 7.18–7.22 (m, 2 H, arom.), 7.27–7.31 (m,
3 H, arom.) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 22.4, 29.4,
35.5, 37.4, 110.1, 125.7, 128.2, 128.5, 142.6, 145.7 ppm. MS (CI,
NH3): m/z (%) = 160 (9) [M]+, 144 (4) [M – 26], 104 (100)
[M – 56]+.
1-Fluoro-4-(2-methylallyl)benzene (Table 2, Entry 4): Following the
Allylbenzene (Table 2, Entry 9): Following the typical experimental
procedure, sulfonyl chloride 2 (0.1 g, 0.71 mmol, 1 equiv.) and
phenylmagnesium chloride (5i; 1.8  in THF, 0.6 mL, 1.1 mmol,
1.5 equiv.) gave the product (65 mg, 78%) as a colorless oil. 1H
typical experimental procedure, sulfonyl chloride
1 (0.1 g,
0.65 mmol, 1 equiv.) and 4-fluorophenylmagnesium bromide (5d;
1.0  in THF, 1.0 mL, 1.0 mmol, 1.5 equiv.) gave the product
(72 mg, 74%) as a light yellow oil. IR (film): ν = 2972, 2909, 1601, NMR (400 MHz, CDCl3): δ = 3.41 (d, J = 6.5 Hz, 2 H, CH2),
˜
1506, 1220, 1156, 1093, 1016, 891, 806, 776, 632, 567 cm–1. 1H
5.06–5.14 (m, 2 H, olefinic), 5.94–6.06 (m, 1 H, olefinic), 7.24–
NMR (400 MHz, CDCl3): δ = 1.69 (s, 3 H, Me), 3.31 (s, 2 H, CH2), 7.32 (m, 3 H, arom.), 7.34–7.42 (m, 2 H, arom.) ppm. 13C NMR
4.73 (s, 1 H, olefinic), 4.82 (s, 1 H, olefinic), 6.96–7.02 (m, 2 H,
arom.), 7.13–7.19 (m, 2 H, arom.) ppm. 13C NMR (100.6 MHz,
CDCl3): δ = 22.4, 43.6, 112.0, 115.0 (d, J = 20.8 Hz), 130.1 (d, J =
(100.6 MHz, CDCl3): δ = 40.5, 115.8, 126.2, 128.4, 128.6, 137.5,
140.1 ppm. MS (CI, NH3): m/z (%) = 118 (81) [M]+, 117 (100)
[M – 1]+, 103 (8) [M – 15]+, 91 (38) [M – 27]+.
Eur. J. Org. Chem. 2009, 6281–6288
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
6285

C. M. R. Volla, D. Markovic´, S. R. Dubbaka, P. Vogel
FULL PAPER
1-Allyl-4-methoxybenzene (Table 2, Entry 10): Following the typical
experimental procedure, sulfonyl chloride 2 (0.1 g, 0.71 mmol,
1 equiv.) and 4-methoxyphenylmagnesium bromide (5c; 1.0  in
THF, 1.1 mL, 1.1 mmol, 1.5 equiv.) gave the product (96 mg, 91%)
as a colorless oil. 1H NMR (400 MHz, CDCl3): δ = 3.39 (d, J =
6.6 Hz, 2 H, CH2), 3.84 (s, 3 H, OMe), 5.08–5.16 (m, 2 H, olefinic),
5.96–6.07 (m, 1 H, olefinic), 6.90 (d, J = 8.6 Hz, 2 H, arom.), 7.16
(d, J = 8.6 Hz, 2 H, arom.) ppm. 13C NMR (100.6 MHz, CDCl3):
δ = 39.4, 55.3, 113.8, 115.4, 129.5, 132.1, 137.9, 158.0 ppm. MS
(CI, NH3): m/z (%) = 149 (8) [M + 1]+, 148 (100) [M]+, 133 (23)
[M – 15], 117 (41) [M – 31]+, 91 (31) [M – 57]+.
3.51 (m, 1 H, CH), 5.02–5.10 (m, 2 H, olefinic), 5.97- 6.07 (m, 1
H, olefinic), 7.09–7.15 (m, 4 H, arom.). MS (CI, NH3): m/z (%) =
147 (7) [M + 1]+, 146 (62) [M]+, 131 (100) [M – 15], 115 (18)
[M – 31]+, 91 (34) [M – 55]+.
1-(But-2-enyl)-4-methoxybenzene and 1-(But-3-en-2-yl)-4-methoxy-
benzene (Table 4, Entries 3 and 6):[43]
Method A: Following the typical experimental procedure, sulfonyl
chloride 3 (0.1 g, 0.65 mmol, 1 equiv.) and 4-methoxyphenylmagne-
sium bromide (5c; 0.5  in THF, 2.0 mL, 1.0 mmol, 1.5 equiv.) gave
the mixture of products (90 mg, 85%) as a colorless oil.
Method B: Following the typical experimental procedure, sulfonyl
chloride 4 (0.1 g, 0.65 mmol, 1 equiv.) and 4-methoxyphenylmagne-
sium bromide (5c; 0.5  in THF, 2.0 mL, 1.0 mmol, 1.5 equiv.) gave
the mixture of products (83 mg, 79%) as a colorless oil.
1-Undecene (Table 2, Entry 11): Following the typical experimental
procedure, sulfonyl chloride 2 (0.1 g, 0.71 mmol, 1 equiv.) and n-
octylmagnesium bromide (5j; 2.0  in Et2O, 0.55 mL, 1.1 mmol,
1.5 equiv.) gave the product (82 mg, 75%) as a colorless oil. 1H
NMR (400 MHz, CDCl3): δ = 0. 88–0.93 (m, 3 H, Me), 1.24–1.35
(m, 12 H, 6 CH2), 1.36–1.44 (m, 2 H, CH2), 2.07–2.10 (m, 2 H,
CH2), 4.92–5.06 (m, 2 H, olefinic), 5.78–5.90 (m, 1 H, olefinic)
ppm. 13C NMR (100.6 MHz, CDCl3): δ = 14.1, 22.7, 28.9, 29.2,
29.3, 29.5, 29.6, 31.9, 33.8, 114.07, 139.3 ppm. MS (CI, NH3): m/z
(%) = 154 (3) [M]+, 126 (6) [M – 28]+, 111 (14) [M – 43]+, 97 (31)
[M – 57]+, 83 (55) [M – 71]+, 69 (68) [M – 85]+, 55 (100)
[M – 99]+.
1
1-(But-2-enyl)-4-methoxylbenzene: H NMR (400 MHz, CDCl3): δ
= 1.73 (dq, J = 6.1, 1.2 Hz, 3 H, Me), 3.31 (d, J = 6.4 Hz, 2 H,
CH2), 3.83 (s, 3 H, OMe), 5.47–5.68 (m, 2 H, olefinic), 6.88 (d, J
= 8.6 Hz, 2 H, arom.), 7.14 (d, J = 8.6 Hz, 2 H, arom.).
1-(But-3-en-2-yl)-4-methoxylbenzene: 1H NMR (400 MHz, CDCl3):
δ = 1.39 (d, J = 7.1 Hz, 3 H, Me), 3.43–3.51 (m, 1 H, CH), 5.04–
5.11 (m, 2 H, olefinic), 6.00- 6.09 (m, 1 H, olefinic), 6.90 (d, J =
8.7 Hz, 2 H, arom.), 7.18 (d, J = 8.7 Hz, 2 H, arom.) ppm. MS
(CI, NH3): m/z (%) = 163 (13) [M + 1]+, 162 (99) [M]+, 147 (100)
[M – 15], 131 (45) [M – 31]+, 115 (50) [M – 47]+, 91 (79)
[M – 71]+.
1-(But-2-enyl)-2-methylbenzene[9] and 1-(But-3-en-2-yl)-2-methyl-
benzene (Table 4, Entries 1 and 4)[9]
Method A: Following the typical experimental procedure, sulfonyl
chloride 3 (0.1 g, 0.65 mmol, 1 equiv.) and o-tolylmagnesium chlo-
ride (5a; 1.0  in THF, 1.0 mL, 1.0 mmol, 1.5 equiv.) gave the mix-
ture of products (71 mg, 75%) as a colorless oil.
2-(2-Methylbenzyl)-2-propenyl Acetate (11a): Following the typical
experimental procedure, sulfonyl chloride 10 (0.3 g, 1.4 mmol,
1 equiv.) and o-tolylmagnesium chloride (5a; 1.0  in THF, 2.2 mL,
2.2 mmol, 1.5 equiv.) gave the product (205 mg, 72%) as a light
Method B: Following the typical experimental procedure, sulfonyl
chloride 4 (0.1 g, 0.65 mmol, 1 equiv.) and o-tolylmagnesium chlo-
ride (5a; 1.0  in THF, 1.0 mL, 1.0 mmol, 1.5 equiv.) gave the mix-
ture of products (68 mg, 72%) as a colorless oil.
yellow oil. IR (film): ν = 2926, 1737, 1372, 1225, 1028, 908, 743,
˜
631, 604, 530 cm–1. 1H NMR (400 MHz, CDCl3): δ = 2.10 (s, 3 H,
Me), 2.27 (s, 3 H, Me-arom.), 3.39 (s, 2 H, CH2), 4.54 (s, 2 H,
OCH2), 4.75 (br. s, 1 H, olefinic), 5.12 (br. s, 1 H, olefinic), 7.12–
7.17 (m, 4 H, arom.) ppm. 13C NMR (100.6 MHz, CDCl3): δ =
19.5, 20.8, 37.3, 67.0, 114.3, 125.9, 126.7, 129.9, 130.2, 136.5, 136.8,
142.4, 170.7 ppm. MS (CI, NH3): m/z (%) = 204 (9) [M]+, 162 (8)
[M – 42]+, 144 (70) [M – 60]+, 129 (100) [M – 75]+, 91 (15)
[M – 133]+. HRMS (ESI-TOF): calcd. for C13H16O2 205.1228;
found 205.1238.
1
1-(But-2-enyl)-2-methylbenzene: H NMR (400 MHz, CDCl3): δ =
1.73 (dq, J = 6.2, 1.4 Hz, 3 H, Me), 2.34 (s, 3 H, Me-arom.), 3.35
(dt, J = 6.3, 1.3 Hz, 2 H, CH2), 5.43–5.54 (m, 1 H, olefinic), 5.57-
5.66 (m, 1 H, olefinic), 7.14–7.21 (m, 4 H, arom.) ppm.
1
1-(But-3-en-2-yl)-2-methylbenzene: H NMR (400 MHz, CDCl3): δ
= 1.40 (d, J = 6.8 Hz, 3 H, Me), 2.39 (s, 3 H, Me-arom.), 3.70–
3.78 (m, 1 H, CH), 5.03–5.12 (m, 2 H, olefinic), 5.98- 6.10 (m, 1
H, olefinic), 7.14–7.21 (m, 4 H, arom.) ppm. MS (CI, NH3): m/z
(%) = 147 (8), [M + 1]+, 146 (54) [M]+, 105 (100), [M – 41]+, 91
(36) [M – 55]+.
2-(4-Methoxybenzyl)-2-propenyl Acetate (11b): Following the typi-
cal experimental procedure, sulfonyl chloride 10 (0.3 g, 1.4 mmol,
1 equiv.) and 4-methoxyphenylmagnesium bromide (5c; 0.5  in
THF, 4.4 mL, 2.2 mmol, 1.5 equiv.) gave the product (206 mg,
1-(But-2-enyl)-4-methylbenzene[41] and 1-(But-3-en-2-yl)-4-methyl-
67%) as a light yellow oil. IR (film): ν = 2933, 1740, 1510, 1373,
˜
benzene (Table 4, Entries 2 and 5):[42]
1245, 1177, 1035, 902, 808, 632, 574 cm–1. 1H NMR (400 MHz,
CDCl3): δ = 2.07 (s, 3 H, Me), 3.35 (s, 2 H, CH2), 3.81 (s, 3 H,
OMe), 4.48 (s, 2 H, OCH2), 4.96 (br. s, 1 H, olefinic), 5.11 (br. s, 1
H, olefinic), 6.84 (d, J = 8.9 Hz, 2 H, arom.), 7.10 (d, J = 8.9 Hz,
2 H, arom.) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 21.1, 39.5,
55.4, 66.4, 113.8, 113.9, 129.8, 130.5, 143.6, 158.2, 170.8 ppm. MS
(CI, NH3): m/z (%) = 221 (4) [M + 1]+, 220 (34) [M]+, 159 (100)
[M – 61]+, 145 (80) [M – 75], 129 (63) [M – 91]+, 91 (25) [M – 129]+.
HRMS (ESI-TOF): calcd. for C13H16O3 221.1178; found 221.1182.
Method A: Following the typical experimental procedure, sulfonyl
chloride 3 (0.1 g, 0.65 mmol, 1 equiv.) and p-tolylmagnesium chlo-
ride (5b; 1.0  in THF, 1.0 mL, 1.0 mmol, 1.5 equiv.) gave the mix-
ture of products (78 mg, 82%) as a colorless oil.
Method B: Following the typical experimental procedure, sulfonyl
chloride 4 (0.1 g, 0.65 mmol, 1 equiv.) and p-tolylmagnesium chlo-
ride (5b; 1.0  in THF, 1.0 mL, 1.0 mmol, 1.5 equiv.) gave the mix-
ture of products (73 mg, 77%) as a colorless oil.
2-Methylene-1,3-dio-tolylpropane (13a): Following the typical ex-
perimental procedure, sulfonyl chloride 12 (0.2 g, 0.8 mmol,
1 equiv.) and o-tolylmagnesium chloride (5a; 1.0  in THF, 2.4 mL,
2.4 mmol, 3.0 equiv.) gave the product (142 mg, 75%) as a light
1
1-(But-2-enyl)-4-methylbenzene: H NMR (400 MHz, CDCl3): δ =
1.71 (dq, J = 6.0, 1.2 Hz, 3 H, Me), 2.35 (s, 3 H, Me-arom.), 3.31
(d, J = 6.3 Hz, 2 H, CH2), 5.47–5.66 (m, 2 H, olefinic), 7.09–7.15
(m, 4 H, arom.).
yellow oil. IR (film): ν = 2921, 1644, 1493, 1460, 1378, 896, 741,
˜
1
1
1-(But-3-en-2-yl)-4-methylbenzene: H NMR (400 MHz, CDCl3): δ 633, 541 cm–1. H NMR (400 MHz, CDCl3): δ = 2.22 (s, 6 H, Me-
= 1.48 (d, J = 7.0 Hz, 3 H, Me), 2.36 (s, 3 H, Me-arom.), 3.42–
arom.), 3.34 (s, 4 H, 2CH2), 4.60 (s, 2 H, olefinic), 7.11–7.17 (m, 8
6286
www.eurjoc.org
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2009, 6281–6288

Ligandless Iron-Catalyzed Desulfinylative C–C Allylation Reactions
H, arom.) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 19.3, 40.2,
112.4, 125.8, 126.4, 129.9, 130.1, 136.8, 137.6, 146.4 ppm. MS (CI,
NH3): m/z (%) = 254 (14) [M + 18]+, 236 (44) [M]+, 221 (11)
[M – 15]+, 144 (25) [M – 92]+, 130 (100) [M – 106]+, 105 (59)
[M – 121]+, 91 (42) [M – 145]+.
[4]
[5]
S. R. Dubbaka, P. Vogel, Org. Lett. 2004, 6, 95–98.
S. R. Dubbaka, P. Vogel, Adv. Synth. Catal. 2004, 346, 1793–
1797.
a) S. R. Dubbaka, P. Vogel, Chem. Eur. J. 2005, 11, 2633–2641;
b) S. R. Dubbaka, D. B. Zhao, Z. F. Fei, C. M. R. Volla, P. J.
Dyson, P. Vogel, Synlett 2006, 3155–3157.
S. R. Dubbaka, P. Vogel, Tetrahedron Lett. 2006, 47, 3345–
3348.
S. R. Dubbaka, P. Vogel, Angew. Chem. Int. Ed. 2005, 44, 7674–
7684.
C. M. R. Volla, S. R. Dubbaka, P. Vogel, Tetrahedron 2009, 65,
504–511.
D. Markovic, C. M. R. Volla, A. Alvarez, J. A. Sordo, P. Vogel,
manuscript in preparation.
A. Alvarez, D. Markovic, P. Vogel, J. A. Sordo, J. Am. Chem.
Soc. 2009, 131, 9547–9561.
C. M. Rao Volla, P. Vogel, Angew. Chem. Int. Ed. 2008, 47,
1305–1307.
M. S. Kharasch, O. Reinmuth, Grignard Reactions of Nonme-
tallic Substances, Prentice-Hall, New York, 1954, p. 1257.
M. Tamura, J. Kochi, J. Organomet. Chem. 1971, 31, 289–309;
see also: M. Tamura, J. Kochi, J. Am. Chem. Soc. 1971, 93,
1487–1489; J. Kochi, Acc. Chem. Res. 1974, 7, 351–360.
J. L. Fabre, M. Julia, J. N. Verpeaux, Tetrahedron Lett. 1982,
23, 2469–2472; see also: E. Alvarez, T. Cuvigny, C. H. Du Pen-
hoat, M. Julia, Tetrahedron 1988, 44, 111–118.
G. A. Molander, B. J. Rahn, D. C. Shubert, S. E. Bonde, Tetra-
hedron Lett. 1983, 24, 5449–5452.
V. Fiandanese, G. Marchese, V. Martina, L. Ronzini, Tetrahe-
dron Lett. 1984, 25, 4805–4808.
[6]
2-Methylene-1,3-diphenylpropane (13b):[44] Following the typical ex-
perimental procedure, sulfonyl chloride 12 (0.2 g, 0.8 mmol,
1 equiv.) and phenylmagnesium chloride (5i; 1.8  in THF,
1.35 mL, 2.4 mmol, 3.0 equiv.) gave the product (118 mg, 71%) as
a colorless oil. 1H NMR (400 MHz, CDCl3): δ = 3.31 (s, 4 H,
[7]
[8]
[9]
2CH2), 4.87 (s, 2 H, olefinic), 7.30–7.35 (m, 10 H, arom.) ppm. 13
C
[10]
[11]
[12]
[13]
[14]
NMR (100.6 MHz, CDCl3): δ = 42.3, 113.4, 126.4, 128.4, 129.1,
139.6, 148.5 ppm. MS (CI, NH3): m/z (%) = 209 (9) [M + 1]+, 208
(52) [M]+, 193 (25) [M – 15], 129 (33) [M – 79]+, 117 (100)
[M – 91]+, 115 (84) [M – 93]+, 91 (67) [M – 117]+.
1,3-Bis(4-methoxyphenyl)-2-methylenepropane (13c): Following the
typical experimental procedure, sulfonyl chloride 12 (0.2 g,
0.8 mmol, 1 equiv.) and 4-methoxyphenylmagnesium bromide (5c;
0.5  in THF, 4.8 mL, 2.4 mmol, 3.0 equiv.) gave the product
(176 mg, 82%) as a colorless oil. IR (film): ν = 2932, 1609, 1508,
˜
1463, 1300, 1242, 1174, 1035, 907, 818, 732, 631 cm–1. 1H NMR
(400 MHz, CDCl3): δ = 3.29 (s, 4 H, 2CH2), 3.86 (s, 6 H, OMe),
4.87 (s, 2 H, olefinic), 6.90 (d, J = 8.9 Hz, 4 H, arom.), 7.13 (d, J
= 8.9 Hz, 2 H, arom.) ppm. 13C NMR (100.6 MHz, CDCl3): δ =
41.2, 55.3, 112.7, 113.8, 130.1, 131.7, 149.2, 158.1 ppm. MS (CI,
NH3): m/z (%) = 268 (91) [M]+, 253 (14) [M – 15], 160 (81)
[M – 108]+, 145 (65) [M – 123]+, 121 (100) [M – 147]+, 91 (31)
[M – 177]+. HRMS (ESI-TOF): calcd. for C18H20O2 269.1541;
found 269.1538.
[15]
[16]
[17]
[18]
a) G. Cahiez, P. Y. Chavant, E. Metais, Tetrahedron Lett. 1992,
33, 5245–5248; b) G. Cahiez, S. Marquais, Tetrahedron Lett.
1996, 37, 1773–1776; c) G. Cahiez, H. Avedissian, Synthesis
1998, 1199–1205; d) G. Cahiez, V. Habiak, C. Duplais, A.
Moyeux, Angew. Chem. Int. Ed. 2007, 46, 4364–4366; e) G.
Cahiez, C. Duplais, A. Moyeux, Org. Lett. 2007, 9, 3253–3254;
f) G. Cahiez, V. Habiak, O. Gager, Org. Lett. 2008, 10, 2389–
2392.
Supporting Information (see footnote on the first page of this arti-
1
cle): Copies of the H and 13C NMR spectra of the compounds.
Acknowledgments
[19]
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Received: August 14, 2009
Published Online: October 29, 2009
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Eur. J. Org. Chem. 2009, 6281–6288