Direct alkenylation of arylamines at the ortho-position with magnesium alkylidene carbenoids and some theoretical studies of the reactions

Article abstract of DOI:10.1016/j.tet.2005.08.035

1-Chlorovinyl p-tolyl sulfoxides were synthesized from ketones and chloromethyl p-tolyl sulfoxide in high yields. Treatment of the sulfoxides with isopropylmagnesium chloride at -78°C in toluene gave magnesium alkylidene carbenoids (α-chloro alkenylmagnesium chlorides), which were treated with N-lithio arylamines to afford ortho-alkenylated arylamines in moderate yields. The reaction, in some cases, proceeded in a highly stereospecific manner at the carbon bearing the chlorine and the sulfinyl group. The structures of the α-chloro alkenylmagnesium chlorides and the reactivity of the N-lithio meta-substituted anilines were studied at the B3LYP and MP2 levels of theory with the 6-31(+)G* basis set. This reaction offers a quite novel and direct alkenylation of arylamines at the ortho-position of the aromatic ring.

Full text of DOI:10.1016/j.tet.2005.08.035

Tetrahedron 61 (2005) 10262–10276
Direct alkenylation of arylamines at the ortho-position with
magnesium alkylidene carbenoids and some theoretical studies
of the reactions
a
b,
Tsuyoshi Satoh,a, Yumi Ogino and Kaori Ando
*
*
aDepartment of Chemistry, Faculty of Science, Tokyo University of Science; Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan
bCollege of Education, University of the Ryukyus, Nishihara-cho, Okinawa 903-0213, Japan
Received 22 July 2005; accepted 5 August 2005
Available online 12 September 2005
Abstract—1-Chlorovinyl p-tolyl sulfoxides were synthesized from ketones and chloromethyl p-tolyl sulfoxide in high yields. Treatment of
the sulfoxides with isopropylmagnesium chloride at K78 8C in toluene gave magnesium alkylidene carbenoids (a-chloro alkenylmagnesium
chlorides), which were treated with N-lithio arylamines to afford ortho-alkenylated arylamines in moderate yields. The reaction, in some
cases, proceeded in a highly stereospecific manner at the carbon bearing the chlorine and the sulfinyl group. The structures of the a-chloro
alkenylmagnesium chlorides and the reactivity of the N-lithio meta-substituted anilines were studied at the B3LYP and MP2 levels of theory
with the 6-31(C)G* basis set. This reaction offers a quite novel and direct alkenylation of arylamines at the ortho-position of the aromatic
ring.
q 2005 Elsevier Ltd. All rights reserved.
1. Introduction
and Yamaguchi et al.3 Sartori’s group synthesized 1,1-di-
arylethylenes directly from substituted anilines and phenyl-
acetylene in the presence of montmorillonite KSF.2
Yamaguchi’s group synthesized ortho-vinylated anilines
directly from anilines with ethyne in the presence of
SnCl4–Bu3N.3
Arylamines, including anilines, are undoubtedly one of the
most important and fundamental compounds in organic
chemistry. Arylamines have been widely used as the
material for medicine, dyes, and other chemical products.
In view of this importance of arylamines, innumerable
studies are still being actively carried out concerning their
chemistry and synthesis.1
We recently reported a new method for the generation of
magnesium alkylidene carbenoids 3 from 1-chlorovinyl
p-tolyl sulfoxides 2, which were synthesized from ketones 1
and chloromethyl p-tolyl sulfoxide in three steps in high
yields,4 with a Grignard reagent5 via a sulfoxide–mag-
nesium exchange reaction.6 From the generated magnesium
alkylidene carbenoids 3, a new method for the synthesis of
tetra-substituted olefins7 and allenes8 was realized.
The alkylation of the aromatic ring of arylamines is quite
important chemistry for the synthesis of derivatives of
arylamines. However, direct alkylation of arylamines
having a free amino group is not a so easily accessible
process. For example, under normal Friedel–Crafts alkyl-
ation conditions, the reaction is inhibited by complex
formation of the amino group with the acid catalyst. An
even more difficult process is the direct alkenylation of the
arylamines. To the best of our knowledge, only two reports
concerning the direct alkenylation of arylamines on the
aromatic ring have been published so far by Sartori et al.2
In continuation of our interest in the development of
new synthetic methods by utilizing the generated
magnesium alkylidene carbenoids 3 in organic synthesis,
we investigated the reaction of 3 with N-lithio amines
and found that the reaction with N-lithio arylamines
gave ortho-alkenylated arylamines 4 in moderate to
good yields (Scheme 1).9 In this paper we describe in
detail the direct alkenylation of arylamines at the ortho-
position with magnesium alkylidene carbenoids and
theoretical studies of the reaction.
Keywords: Sulfoxide–magnesium exchange reaction; Magnesium alkyli-
dene carbenoid; Alkenylation; ortho-Alkenylated arylamine; Theoretical
study.
Corresponding authors. Tel.: C81 3 5228 8272; fax: C81 3 3235 2214;
e-mail: tsatoh@ch.kagu.tus.ac.jp
*
0040–4020/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2005.08.035

T. Satoh et al. / Tetrahedron 61 (2005) 10262–10276
10263
Scheme 1.
2. Results and discussion
and n-BuLi in THF at K78 8C, was added to the solution of
the magnesium alkylidene carbenoid 6, generated as above,
through a cannula at K78 8C and the temperature of the
reaction mixture was gradually allowed to warm to K10 8C.
We obtained a colorless crystalline product in 25% yield.
The product showed C15H19NO2 as the molecular formula
and N–H absorption on its IR spectrum. At this stage two
products, alkenyl aniline 7a and enamine 8, were expected
to be produced. 1H NMR showed two NH protons and only
four aromatic protons (d 6.69 (1H, d), 6.73 (1H, t), 6.98 (1H,
d), 7.06 (1H, t)). From the coupling pattern of these aromatic
protons and the 13C NMR, the structure of the product was
unambiguously determined to be the ortho-alkenylated
aniline 7a (Scheme 2).
2.1. Direct ortho-alkenylation of arylamines including
aniline with the magnesium alkylidene carbenoid 6
1-Chlorovinyl p-tolyl sulfoxide 5, which was synthesized
from 1,4-cyclohexanedione mono ethylene ketal and
chloromethyl p-tolyl sulfoxide in high yield,4,7 in dry THF
was treated with t-BuMgCl (0.12 equiv) at K78 8C to
remove a trace of moisture in the reaction mixture. After
10 min, i-PrMgCl (2.8 equiv) was added to the reaction
mixture. The sulfoxide–magnesium exchange reaction took
place instantaneously to give the magnesium alkylidene
carbenoid 6.8b First, reaction of 6 with N-lithio piperidine
and N-lithio n-hexylamine was investigated, however, only
a rather complex mixture was obtained with these N-lithio
alkylamines.
We were somewhat surprised and pleased by this result
because no report has been published on the reaction of
anilines with alkylidene carbenes (or carbenoids).10 In
addition, this reaction was recognized to be a quite novel
and direct alkenylation of arylamines on the aromatic ring.
Next, the reaction was investigated with N-litho arylamines.
N-litho aniline (3 equiv), which was generated from aniline
Scheme 2.
Table 1. Conditions for the ortho-alkenylation of aniline
Entry
Solvent
Additive
Yield of 7a %
1
2
3
4
5
6
7
8
9
THF
No
No
No
25
9
CPMEa
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
49
14
14
16
25
37
40
DMPUb
HMPA
12-Crown-6
TMEDA
DME
CPMEa
a Cyclopentyl methyl ether.
b 1,3-Dimethyl-3,4,5,6-tetrahydro-2(1H)pyrimidinone.

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T. Satoh et al. / Tetrahedron 61 (2005) 10262–10276
Table 2. Synthesis of ortho-alkenylated arylamines 7 by the reaction of magnesium alkylidene carbenoid 6 with N-lithio arylamines
Entry
1
Arylaminea
ortho-Alkenylated arylamine 7
(Yield, %)
(44)
7b XZOCH3
7c XZCl
(28)
2
3
4
(32)
7d
b
—
5
6
7
(38)
(66)
(60)
7e
7f
7g
a Three equivalents of N-lithio arylamines were reacted with 6.
b No para-alkenylated product was obtained.
First of all, we investigated the best conditions for this
ortho-alkenylation and the results are summarized in
Table 1.
N-Methylaniline gave an ortho-alkenylated product 7e in
38% yield (entry 5). Interestingly, the reaction with
1-aminonaphthalene and 1-aminoanthracene gave much
better yields of the ortho-alkenylated aryl amines 7f and 7g,
respectively, (entries 6 and 7).
The use of cyclopentyl methyl ether (CPME) as a solvent
gave a miserable yield (entry 2). As shown in entry 3,
toluene was found to be a good solvent for the reaction and
49% yield of 7a was obtained. Encouraged by this result,
several reaction conditions were investigated in toluene in
the presence of an additive. However, the additives
investigated were found to be ineffective (entries 4–9).
We decided to use toluene as the solvent without any
additive throughout this study.
The reaction of the magnesium alkylidene carbenoid 6 with
meta-substituted anilines is quite interesting because the
regioisomers are expected to be obtained. We investigated
the reaction with four meta-substituted anilines and the
results are summarized in Table 3.
The reaction with meta-anisidine gave two products and the
main product was found to have the alkenyl group at a more
hinderedposition7h(entry1). Inthepreviouscommunication,
we reported that the reason for this regioselectivity may be the
chelation of the magnesium alkylidene carbenoid 6 between
the amino group and the methoxy group.9 However, all other
meta-substitutedanilines,evenmeta-methylaniline, whichhas
no ability for the chelation, gave more hindered alkenylated
compounds asmain products(entries2–4), althoughthe yields
were not satisfactory. The theoretical study for this
regioselectivity is discussed later (vide infra).
Next, we investigated the generality of this reaction of
the magnesium alkylidene carbenoid 6 with other
N-lithio arylamines under the conditions described
above and the results are summarized in Table 2. The
reaction with the aniline having an electron-donating
group (OCH3) at the 4-position gave a similar yield of
7b (entry 1), however, the aniline having an electron-
withdrawing group (Cl) gave 7c in markedly diminished
yield (entry 2). The reaction with ortho-toluidine gave
the ortho-alkenylated aniline 7d (entry 3). Interestingly,
2,6-dimethylaniline gave no para-alkenylated aniline.
This result indicated that this reaction only gives ortho-
alkenylated products.
2.2. Study for the reaction mechanism
At this stage, we investigated the mechanism of this reaction

T. Satoh et al. / Tetrahedron 61 (2005) 10262–10276
10265
Table 3. Synthesis of ortho-alkenylated arylamines 7 by the reaction of magnesium alkylidene carbenoid 6 with meta-substituted N-lithio anilines
Entry
meta-Substituted anilina
ortho-Alkenylated arylamine 7
(Yield, %)
1
7h (30)
7i (13)
2
3
4
7j (19)
7k (14)
7m (13)
7o (4)
7l (25)
7n (7)
a Three equivalents of meta-substituted N-lithio aniline was reacted with 6.
by using aniline-2,3,4,5,6-d5 (Scheme 3). The reaction
of the magnesium alkylidene carbenoid 6 with N-lithio
aniline-2,3,4,5,6-d5 A was carried out in toluene and
ortho-alkenylated aniline 9 was obtained. The deuterium
incorporation of 9 at the olefinic carbon was measured by 1H
NMR and the deuterium incorporation was found to be 25%.
From this result, we propose the mechanism of this reaction
as follows (Scheme 3).
The N-lithio arylamine A is present in the resonance form,
Scheme 3.

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T. Satoh et al. / Tetrahedron 61 (2005) 10262–10276
Table 4. Synthesis of ortho-alkenylated arylamines by the reaction of magnesium alkylidene carbenoid derived from 10 with N-lithio arylamines
Entry
Arylaminea
ortho-Alkenylated arylamine
(Yield, %)
1
2
11a XZH
11b XZOCH3
(43)
(43)
3
11c (29)
11d (22)
4
5
(46)
(81)
11e
11f
6
(79)
11g
a Three equivalents of N-lithio arylamine was reacted with the carbenoid derived from 10.
lithium a-imino carbanion B. The reaction of B with the
magnesium alkylidene carbenoid 6 takes place with
inversion of the configuration at the carbenoid carbon to
give the intermediate C. The inversion of the configuration
in the reaction of lithium alkylidene carbenoids with
alkyllithium has been reported by Walborsky et al.11 Oku
et al.12 and Narasaka et al.13 We will discuss later the
structure of the carbenoid and the reaction by B3LYP and
MP2 calculations (vide infra).
imine F to give an anion having deuterium on the olefinic
carbon G. The intermediate G is aromatized to give E.
Close to 100% deuterium incorporation was expected in
path b. As described above, because the obtained ortho-
alkenylated aniline 9 had 25% of deuterium on the olefinic
carbon, this reaction was proved to proceed via path a.
2.3. Synthesis of the aryl amines having 2-methyl-1-
propene at the ortho-position
Two pathways (path a and b) were postulated for the
mechanism from the intermediate C to the product 9. Thus,
the intermediate C is first aromatized (intermolecular
transfer of the deuterium from the carbon to the nitrogen
was presumed to be take place) to give the alkenylmag-
nesium D. Then the alkenyl anion picks up the proton or
deuterium on the nitrogen to give E, which was treated with
water to afford 9 (path a). Less than 50% deuterium
incorporation on the olefinic carbon was anticipated in path
a. The other mechanism (path b) is as follows: the alkenyl
anion first picks up the deuterium on the carbon next to the
To investigate the generality of this reaction, we further
studied this reaction using 1-chlorovinyl p-tolyl sulfoxide
10 derived from acetone and the results are summarized in
Table 4. Entries 1 and 2 show that quite similar yields were
obtained with aniline and p-anisidine. The reaction with
m-anisidine gave two products and the main product was
again found to be the more sterically hindered 11c (entry 3).
N-methylaniline gave better yield compared with the result
in Table 2, entry 5. Again, much better yields were obtained
from the reaction of the magnesium alkylidene carbenoid with
1-aminonaphthalene and 1-aminoanthracene (entries 5 and 6).

T. Satoh et al. / Tetrahedron 61 (2005) 10262–10276
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Table 5. The reaction of the magnesium alkylidene carbenoids derived from E- and Z-1-chlorovinyl p-tolyl sulfoxides with N-lithio aniline, N-lithio 1-
aminonaphthalene and N-lithio 1-aminoanthracene
Entry
Arylaminea
Product
E/Zb
(Yield, %)
1
6:94
(53)
12E
16Z
16E
17Z
17E
18Z
18E
19Z
19E
2
94:6
(46)
(65)
(71)
(69)
(66)
(68)
(62)
(54)
(55)
(61)
(45)
12Z
12E
3
3:97
4
12Z
12E
12Z
95:5
5
22:78
84:16
4:96
6
7
13E
13Z
8
94:6
9
44:56
34:66
6:94
14E
20E
20Z
21E
21Z
10
11
12
14Z
15E
15Z
25:75
a Three equivalents of N-lithio aniline, N-lithio 1-aminonaphthalene and N-lithio 1-aminoanthracene were reacted with the magnesium alkylidene carbenoids.
b The ratio of E/Z was determined from their 1H NMR.

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T. Satoh et al. / Tetrahedron 61 (2005) 10262–10276
Table 6. Quenching of the magnesium alkylidene carbenoid derived from 12 and 15 with water
Entry
1
1-Chlorovinyl p-tolyl sulfoxide
Alkenylchloride
22E
22Z
23E
12E
12Z
2
3
15E
15Z
4
23Z
23E:23ZZ35:65
2.4. Stereochemistry of the reaction
also the ortho-alkenylated 1-aminoanthracenes, 18Z and
18E, stereospecifically although the stereospecificity was
somewhat lower (entries 5 and 6). The 1-chlorovinyl p-tolyl
sulfoxide derived from methyl vinyl ketone 13 showed
again quite high stereospecificity with 1-aminonaphthalene
to give 19Z and 19E (entries 7 and 8).
Next, we investigated the stereochemistry of these
reactions. First of all, stereoisomers of the 1-chlorovinyl
p-tolyl sufoxides (12–15) were synthesized from unsym-
metrical ketones (2-cyclohexenone, methyl vinyl ketone,
2-heptanone, and acetophenone) and the reaction was
carried out with aniline, 1-aminonaphthalene and 1-amino-
anthracene. The results are summarized in Table 5. Quite
interestingly, the reaction of the magnesium alkylidene
carbenoids derived from 12E and 12Z with aniline and
1-aminonaphthalene gave Z-ortho-alkenylated arylamines
16Z and 17Z, and E-ortho-alkenylated arylamines 16E and
17E, respectively, with high stereospecificity (entries 1–4).
The reaction of 12E and 12Z with 1-aminoanthracene gave
Further, this reaction was carried out with the 1-chlorovinyl
p-tolyl sulfoxides derived from unsymmetrical dialkyl
ketone (2-heptanone) 14 and alkyl aryl ketone (aceto-
phenone) 15 with 1-aminonaphthalene. Quite interestingly,
both vinyl sulfoxides 14E and 14Z gave mainly Z-isomer
20Z (entries 9 and 10), namely, the reactions with 14 show
stereoselectivity. The reaction with 15E and 15Z showed
also stereoselectivity. In this case, 15E exclusively gave 21Z
Figure 1. Geometries of 1-chloro-2-methylpropenylmagnesium chloride 24 optimized at the RHF, B3LYP, and MP2 levels of theory with the 6-31(C)G* and
6-311(C)G** basis sets. The energies of these geometries were calculated at the CCSD(T) method with the corresponding basis set.

T. Satoh et al. / Tetrahedron 61 (2005) 10262–10276
10269
in high stereoselectivity (entry 11). The reaction with 15Z
gave 21Z, however, the selectivity was lower than the
reaction with 15E (entry 12).
alkenylmagnesium chlorides were first studied using
the RHF, B3LYP, and MP2 levels of theory with the
6-31(C)G*15 basis set. The obtained geometries of
1-chloro-2-methylpropenyl-magnesium chloride 24 are
shown in Figure 1.
The stereospecificity and the stereoselectivity mentioned
above are explained as follows. If the configuration of the
magnesium alkylidene carbenoids generated from 1-chloro-
vinyl p-tolyl sulfoxides derived from a,b-unsaturated
ketones is stable enough in the reaction conditions, the
N-lithio arylamine attacks backside to the chlorine atom to
give the product stereospecifically. On the other hand, if the
configuration of the magnesium alkylidene carbenoids
generated from the 1-chlorovinyl p-tolyl sulfoxide derived
from dialkyl ketone or alkyl aryl ketone is not stable under
the reaction conditions, both isomers of the magnesium
alkylidene carbenoids are present in equilibrium before the
alkenylation and from the more stable isomer the main
product is produced.
The magnesium atom interacts with the vinyl chloride
strongly at the RHF level and the structure is a complex of
the alkenyl carbene with MgCl2 rather than the a-chloro
alkenylmagnesium chloride. This structure is not com-
patible with our experimental results. On the other hand,
both the B3LYP and MP2 geometries are the a-halo
alkenylmagnesium chloride where the C–Cl bond is bridged
by the magnesium atom. The 13C NMR study16,17 of the
a-bromo alkyllithium compounds showed considerable
weakening of the C–Br bonds and the theoretical studies
reported a bridging geometry for H2CLiCl,18 CH2]FLi,19
and RR0C]CLiX (XZCl, Br).13
In order to obtain the information on the stability of the
magnesium alkylidene carbenoids, we treated 12 and 15
with i-PrMgCl at K78 8C for 5 min and the generated
magnesium alkylidene carbenoids were quenched with
water. The results are summarized in Table 6. As
anticipated, the reaction of 12E and 12Z gave 22E and
22Z, respectively, without any presence of the isomer
(entries 1 and 2). These results imply that the configuration
of the generated magnesium alkylidene carbenoids is stable
for at least 5 min. The reaction of 15E gave 23E exclusively,
however, 15Z gave a mixture of 23E and 23Z. These results
imply that the magnesium alkylidene carbenoid generated
from 15E and 15Z is unstable.7 These results are consistent
with the stereospecificity and the stereoselectivity shown in
Table 5. We studied the stability for the geometry of the
magnesium alkylidene carbenoids by calculation and will
discuss this later (vide infra).
In order to know, which a-chloro alkenylmagnesium
chloride structure is more reliable, the energies were
computed using a higher level of the correlation method,
CCSD(T)/6-31(C)G*, on these geometries. The relative
energies are C2.03, 0.28, and 0 kcal/mol, respectively.
Although the Cl–Mg distance of the MP2 geometry is longer
than that of the B3LYP by 0.26 A, those CCSD(T) energies
are not much different. The MP2 geometry was reoptimized
with constraining the Cl–Mg distance to 2.45, 2.50, and
˚
˚
2.55 A at the MP2/6-31(C)G* level and the relative
CCSD(T) energies were K0.09, K0.13 and K0.08 kcal/
mol, respectively. Therefore, the real structure seems to be
between the B3LYP structure and the MP2 structure and is
closer to the latter. To see the basis set effects, the structures
were also calculated using 6-311(C)G**. Since the
geometries are almost the same as the 6-31(C)G* basis
for all the RHF, B3LYP, and MP2 levels of theory, the
6-31(C)G* basis set is as good as the 6-311(C)G** basis
set for the structure of a-chloro alkenylmagnesium chloride.
2.5. Theoretical studies for the a-chloro alkenylmag-
nesium chlorides and the reactivity of the N-lithio meta-
substituted anilines
Stereospecific formation of the alkenyl aniline was observed
when the conjugated a-chloro alkenylmagnesium chlorides
were used. Therefore, the structures of the conjugated
a-chloro alkenylmagnesium chlorides were further studied.
The optimized structures for E- and Z-1-chloro-2-methyl-1,
3-butadienylmagnesium chloride 25 are shown in Figure 2.
There are three characteristic differences between 24 (see
Fig. 1) and 25. The distances between the Mg and the vinyl-
Cl is much longer, the C–Cl bond is shorter, and the C]C–
To better understand these substitution reactions of the
magnesium alkylidene carbenoids (a-chloro alkenylmag-
nesium chlorides), we studied them computationally. All
calculations were performed using the Gaussian 98
program.14 The frequency calculations on the optimized
structures gave only harmonic frequencies and confirmed
that they are minima. The structures of the a-chloro
Figure 2. Geometries of E-25, Z-25, and 26 optimized at the B3LYP/6-31(C)G*, and MP2/6-31(C)G*, and MP2/6-311(C)G**.

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T. Satoh et al. / Tetrahedron 61 (2005) 10262–10276
Figure 3. Optimized structures of N-lithio meta-substituted anilines 27 at the MP2/6-31(C)G* level of theory. Atomic charges with hydrogens summed into
heavy atoms were calculated using the CHelpG scheme of Breneman (MP2/6-31(C)G* densityZMP2 popZCHelpG).
Mg angle is smaller in 25 at both the B3LYP and MP2 levels
of theory. Thus, the conjugated systems are geometrically
stabilized. The charges computed by natural population
analysis (MP2/6-31(C)G* densityZMP2 popZNPA)
show a more negative charge on the vinyl-Cl in 24 and
the alkyl-Cl in 2-chloro-2-propanylmagnesium chloride 26
than on the vinyl-Cl in 25 (the values are as follows: E-25,
K0.06; Z-25, K0.07; 24, K0.18; 26, K0.22).20 In these
cases, the Mg–Cl distances correspond to the amount of
the negative charge on the vinyl-Cl. That is, the shorter the
Mg–Cl distances, the more negative charge on the Cl. Only
a small amount of the negative charge is placed on the vinyl-
Cl due to the charge delocalization in the conjugated
systems 25. Thus, the interaction between the Mg and the Cl
is weaker in 25 than those in 24 and 26. This weaker
interaction increases the geometrical stabilization, and,
therefore, stereospecific reaction can be expected.
31(C)G* densityZMP2 popZCHelpG) were calculated
with the structures optimized at the MP2/6-31(C)G* level.
The results are shown in Figure 3.
Four conformers 27a-1–27a-4 were obtained for N-lithio
meta-anisidine. The more negative atom charge (K0.56)
was found on the carbon-2 in the most stable conformer
27a-1. The same value (K0.49) was obtained on both the
carbon-2 and the carbon-6 in 27a-2, which is 0.22 kcal/mol
less stable than 27a-1. In the other two conformers (27a-3
and 27a-4), the more negative charge was also found on the
carbon-2. Thus, the obtained product selectivity corre-
sponds well to the negative charges on both the carbon-2
and the carbon-6, and the conformer stability.
There are two conformers for N-lithio meta-methylaniline
(27b-1 and 27b-2). Although the more negative charge was
found on the carbon-2 in both conformers, the difference is
small in the more stable 27b-2. Therefore, the less selective
formation of 7j was found (see Table 3, entry 2). There are
also two conformers for both N-lithio meta-chloroaniline
and N-lithio meta-cyanoaniline (27c and 27d). The more
negative charges were found on the carbon-2 in the more
For the reaction with meta-substituted anilines, the more
hindered alkenylated compounds were obtained as main
products. To see the reactivity of these N-lithio meta-
substituted anilines 27, the electrostatic potential-derived
charges using the CHelpG scheme of Breneman (MP2/6-

T. Satoh et al. / Tetrahedron 61 (2005) 10262–10276
10271
stable conformers 27c-1 and 27d-1. Compared to 27a, the
less negative charges found in 27c and 27d are thought to be
a reason for the lower product yields. In these cases, all
the more stable conformers have smaller dipole moment.
Since the reaction was performed in toluene with low
polarity (3Z2.379), the conformers with lower dipole
moment are stabilized. In fact, the energy differences are
in proportion to the differences of the dipole moment in
27b–d.
solvent, the product was purified by silica gel column
chromatography to give 7a (35.9 mg; 49%) as colorless
needles; mp 118–119 8C (AcOEt/hexane); IR (KBr) 3464
(NH), 3371 (NH), 2946, 2894, 1631, 1491, 1454, 1116,
1
1079, 1029, 904, 754 cmK1; H NMR d 1.67 (2H, t, JZ
6.4 Hz), 1.80 (2H, t, JZ6.4 Hz), 2.35 (2H, t, JZ6.6 Hz),
2.46 (2H, dt, JZ6.4 Hz), 3.67 (2H, br s), 3.98 (4H, s), 6.09
(1H, s), 6.69 (1H, d, JZ8.0 Hz), 6.73 (1H, t, JZ7.5 Hz),
6.98 (1H, d, JZ7.4 Hz), 7.06 (1H, t, JZ7.0 Hz). 13C NMR d
26.3, 33.6, 35.5, 36.3, 64.4 (2C), 108.7, 115.0, 118.0, 119.2,
123.6, 127.7, 130.1, 142.4, 144.3. MS m/z (%) 245 (MC,
100), 200 (30), 183 (19), 159 (27), 144 (44), 130 (39), 107
(70), 106 (45). Anal. Calcd for C15H19NO2: C, 73.44; H,
7.81; N 5.71. Found: C, 72.99; H, 7.75; N, 5.48.
For 27a, not only the dipole moment, but also the MeO
conformation is important for the conformer stability. The
electrostatic interaction of the lithium with the carbon-2 and
the oxygen stabilizes 27a-1. On the other hand, this
stabilization was reduced in 27a-4 due to the electrostatic
interaction between the negative carbon-2 and the positive
methyl group. The electrostatic repulsion between the
carbon-2 and the oxygen destabilizes 27a-3 compared
with 27a-2. Furthermore, the dipole moment increases in the
order of 27a-1, 27a-2, 27a-3, and 27a-4. Thus, the energy
differences of these conformers can be explained on the
basis of the dipole moment and the electrostatic interaction.
The electrostatic potential-derived charges were also
calculated for N-lithio aniline 27e and anisole 27f. The
strongly electron-donating lithioamino group increases the
negative charge on both the ortho positions with the lithium
side more. Thus, the CHelpG results explain the experi-
mental reactivity and the selectivity very well.
3.1.2. 2-(1,4-Dioxaspiro[4.5]dec-8-ylidenemethyl)-4-
methoxyphenylamine (7b). Colorless oil; IR (neat) 3445
(NH), 3362 (NH), 2948, 1604, 1498, 1274, 1239, 1120,
1082, 1035 cmK1 1H NMR d 1.67 (2H, t, JZ6.4 Hz),
;
1.80 (2H, t, JZ6.6 Hz), 2.37 (2H, t, JZ6.1 Hz), 2.45 (2H,
t, JZ6.1 Hz), 3.43 (2H, br s), 3.74 (3H, s), 3.98 (4H, m),
6.09 (1H, s), 6.58 (1H, d, JZ2.8 Hz), 6.65 (1H, s), 6.67
(1H, d, JZ2.8 Hz). MS m/z (%) 275 (MC, 100), 230 (22),
212 (8), 189 (15), 174 (22), 160 (16), 137 (55), 122 (15), 117
(8). Calcd for C16H21NO3: M, 275.1520. Found: m/z
275.1523.
3.1.3. 4-Chloro-2-(1,4-dioxaspiro[4.5]dec-8-ylidene-
methyl)phenylamine (7c). Colorless oil; IR (neat) 3469
(NH), 3369 (NH), 2951, 2884, 1615, 1488, 1275, 1248,
1120, 1082, 1033 cmK1; 1H NMR d 1.67 (2H, t, JZ6.6 Hz),
1.79 (2H, t, JZ6.6 Hz), 2.33 (2H, t, JZ6.6 Hz), 2.45 (2H, t,
JZ6.6 Hz), 3.66 (2H, br s), 3.98 (4H, s), 6.01 (1H, s), 6.61
(1H, d, JZ8.5 Hz), 6.94 (1H, d, JZ2.4 Hz), 7.00 (1H, dd,
JZ8.4, 2.5 Hz). MS m/z (%) 279 (MC, 98), 234 (28), 218
(14), 193 (20), 178 (22), 164 (36), 158 (28), 141 (100), 130
(12), 121 (18), 95 (20), 86 (12), 77 (10), 55 (12), 42 (12).
Calcd for C15H18ClNO2: M, 279.1025. Found: m/z
279.1025.
3. Experimental
3.1. General
1
All melting points are uncorrected. H NMR spectra were
measured in a CDCl3 solution with JEOL JNM-LA 500
spectrometer. Electron-impact mass spectra (MS) were
obtained at 70 eV by direct insertion. Silica gel 60 (Merck)
containing 0.5% fluorescence reagent 254 and a quartz
column were used for column chromatography and the
products having UV absorption were detected by UV
irradiation. In experiments requiring a dry solvent, toluene
was distilled from CaH2 and THF was distilled from
diphenylketyl.
3.1.4. 2-(1,4-Dioxaspiro[4.5]dec-8-ylidenemethyl)-6-
methylphenylamine (7d). Colorless crystals; mp 105–
106 8C (AcOEt/hexane); IR (KBr) 3454 (NH), 3369 (NH),
2954, 2879, 2853, 1625, 1588, 1477, 1464, 1119, 1083,
1
1031, 919, 751 cmK1; H NMR d 1.66 (2H, t, JZ6.6 Hz),
5,7 10,21 12E,4 12Z,4 15E,7 and 15Z7 are known compounds.
1.80 (2H, t, JZ6.4 Hz), 2.18 (3H, s), 2.35 (2H, t, JZ
6.4 Hz), 2.46 (2H, t, JZ6.4 Hz), 3.65 (2H, br s), 3.98 (4H,
m), 6.11 (1H, s), 6.67 (1H, t, JZ7.3 Hz), 6.87 (1H, d, JZ
7.3 Hz), 6.97 (1H, d, JZ7.3 Hz). MS m/z (%) 259 (MC,
100), 214 (28), 196 (12), 186 (6), 173 (33), 158 (46), 144
(36), 130 (10), 121 (62), 99 (6). Calcd for C16H21NO2: M,
259.1570. Found: m/z 259.1570. Anal. Calcd for
C16H21NO2: C, 74.10; H, 8.16; N 5.40. Found: C, 73.97;
H, 8.12; N, 5.37.
3.1.1. 2-(1,4-Dioxaspiro[4.5]dec-8-ylidenemethyl)phenyl-
amine (7a). To a solution of 5 (98.1 mg; 0.3 mmol) in
6 mL of dry toluene in a flame-dried flask at K78 8C under
argon atmosphere was added t-BuMgCl (0.036 mmol)
dropwise with stirring. After 10 min, i-PrMgCl
(0.84 mmol) was added dropwise to the reaction mixture
at K78 8C to give the magnesium alkylidene carbenoid 6.
n-BuLi (0.93 mmol) was added to a solution of aniline
(0.082 mL; 0.90 mmol) in 4 mL of dry toluene in an another
flame-dried flask at K78 8C under argon atmosphere to give
the lithium anilide. This solution was added to a solution of
the carbenoid 6 through a cannula. Temperature of the
reaction mixture was gradually allowed to warm to K10 8C.
The reaction was quenched by satd aq NH4Cl and the whole
was extracted with CHCl3. The organic layer was washed
once with water and dried over MgSO4. After removal of the
3.1.5. [2-(1,4-Dioxaspiro[4.5]dec-8-ylidenemethyl)phe-
nyl]methylamine (7e). Colorless crystals; mp 70–71 8C
(hexane); IR (KBr) 3424 (NH), 2947, 2884, 2813, 1601,
1
1578, 1507, 1166, 1120, 1082, 1034, 909, 749 cmK1; H
NMR d 1.65 (2H, t, JZ6.6 Hz), 1.80 (2H, t, JZ6.6 Hz),
2.33 (2H, t, JZ6.6 Hz), 2.45 (2H, t, JZ6.6 Hz), 2.86 (3H,
s), 3.79 (1H, br s), 3.98 (4H, m), 6.03 (1H, s), 6.62 (1H, d,
JZ8.3 Hz), 6.68 (1H, dt, JZ7.4, 0.9 Hz), 6.96 (1H, d, JZ

10272
T. Satoh et al. / Tetrahedron 61 (2005) 10262–10276
7.4 Hz), 7.18 (1H, dt, JZ8.3, 1.2 Hz). MS m/z (%) 259
(MC, 100), 214 (24), 173 (24), 158 (50), 144 (28), 130 (18),
120 (42), 99 (11), 91 (11), 77 (6). Calcd for C16H21NO2: M,
259.1571. Found: m/z 259.1574. Anal. Calcd for
C16H21NO2: C, 74.10; H, 8.16; N, 5.40. Found: C, 73.67;
H, 7.89; N, 5.40.
IR (neat) 3468 (NH), 3370 (NH), 2948, 2884, 1610, 1466,
1120, 1083, 757 cmK1 1H NMR (vinylic proton and
;
aromatic protons of 7j) d 5.95 (s), 6.55 (d, JZ7.9 Hz),
1
6.60 (d, JZ7.3 Hz), 6.96 (t, JZ7.8 Hz); H NMR (vinylic
proton and aromatic protons of 7k) d 6.06 (s), 6.52 (s),
6.55 (d, JZ7.9 Hz), 6.86 (d, JZ7.7 Hz). MS m/z (%) 259
(MC, 100), 214 (38), 173 (30), 158 (54), 144 (48), 120 (80).
Calcd for C16H21NO2: M, 259.1572. Found: m/z 259.1577.
3.1.6.
2-(1,4-Dioxaspiro[4.5]dec-8-ylidenemethyl)
naphthalen-1-ylamine (7f). Colorless needles; mp 123–
124 8C (AcOEt/hexane); IR (KBr) 3472 (NH), 3383 (NH),
2948, 2883, 1615, 1566, 1432, 1403, 1120, 1080, 1033, 758,
735 cmK1; 1H NMR d 1.67 (1H, t, JZ6.4 Hz), 1.84 (1H, t,
JZ6.4 Hz), 2.35 (2H, t, JZ6.6 Hz), 2.52 (2H, t, JZ6.5 Hz),
3.96–4.00 (4H, m), 4.21 (2H, br s), 6.28 (1H, s), 7.15 (1H, d,
JZ8.6 Hz), 7.27 (1H, d, JZ8.3 Hz), 7.41–7.44 (2H, m),
7.76–7.77 (1H, m), 7.81–7.82 (1H, m). MS m/z (%) 295
(MC, 100), 250 (20), 234 (6), 232 (8), 208 (10), 194 (20),
180 (35), 156 (82). Calcd for C19H21NO2: M, 295.1570.
Found: m/z 295.1562. Anal. Calcd for C19H21NO2: C, 77.26;
H, 7.17; N, 4.74. Found: C, 77.15; H, 7.16; N, 4.75.
3.1.11. 3-Chloro-2-(1,4-dioxaspiro[4.5]dec-8-ylidene-
methyl)phenylamine (7l). Colorless oil; IR (neat) 3474
(NH), 3368 (NH), 2952, 2884, 1615, 1471, 1447, 1120,
1083, 1034, 908 cmK1; 1H NMR d 1.65–1.70 (2H, m), 1.78–
1.84 (2H, m), 2.12–2.16 (2H, m), 2.48–2.52 (2H, m), 3.79
(2H, br s), 3.95–4.00 (4H, m), 5.92 (1H, s), 6.58 (1H, d, JZ
8.0 Hz), 6.77 (1H, d, JZ8.0 Hz), 6.97 (1H, t, JZ8.0 Hz).
MS m/z (%) 279 (MC, 100), 234 (26), 218 (18), 193 (28),
178 (32), 164 (42), 158 (23), 141 (73). Calcd for
C15H18ClNO2: M, 279.1024. Found: m/z 279.1018.
3.1.12. 5-Chloro-2-(1,4-dioxaspiro[4.5]dec-8-ylidene-
methyl)phenylamine (7m). Colorless oil; IR (neat) 3469
(NH), 3371 (NH), 2948, 2883, 1608, 1466, 1120, 1083,
3.1.7. 2-(1,4-Dioxaspiro[4.5]dec-8-ylidenemethyl)
anthracen-1-ylamine (7g). Colorless amorphous; IR
(KBr) 3469 (NH), 3390 (NH), 2944, 2879, 1610, 1428,
1
1034, 908, 758 cmK1; H NMR d 1.65 (2H, t, JZ6.6 Hz),
1
1383, 1119, 1087, 1035, 909, 870, 737 cmK1; H NMR d
1.79 (2H, t, JZ6.6 Hz), 2.31 (2H, t, JZ6.6 Hz), 2.44 (2H, t,
JZ6.6 Hz), 3.73 (2H, br s), 3.98 (4H, m), 6.00 (1H, s), 6.67
(1H, s), 6.68 (1H, d, JZ8.3 Hz), 6.87 (1H, d, JZ8.3 Hz).
MS m/z (%) 279 (MC, 100), 250 (8), 234 (26), 220 (8), 217
(20), 193 (26), 178 (29), 164 (38), 158 (20), 141 (65). Calcd
for C15H18ClNO2: M, 279.1024. Found: m/z 279.1022.
1.70 (2H, t, JZ6.6 Hz), 1.86 (2H, t, JZ6.4 Hz), 2.39 (2H, t,
JZ6.1 Hz), 2.54 (2H, t, JZ6.1 Hz), 3.97–4.01 (4H, m),
4.36 (2H, br s), 6.32 (1H, s), 7.16 (1H, d, JZ8.6 Hz), 7.41–
7.46 (3H, m), 7.95–7.97 (1H, m), 7.98–8.0 (1H, m), 8.34
(1H, s), 8.38 (1H, s). MS m/z (%) 345 (MC, 100), 300 (15),
243 (15), 206 (60), 193 (6). Calcd for C23H23NO2: M,
345.1717. Found: m/z 345.1707.
3.1.13. 3-Amino-2-(1,4-dioxaspiro[4.5]dec-8-ylidene-
methyl)benzonitrile (7n). Colorless oil; IR (neat) 3472
(NH), 3369 (NH), 2953, 2885, 2272 (CN), 1621, 1463,
1121, 1084, 1033, 909 cmK1; 1H NMR d 1.68–1.84 (4H, m),
2.21 (2H, m), 2.58 (2H, m), 3.88 (2H, br s), 3.95–3.99 (4H,
m), 6.06 (1H, s), 6.86 (1H, dd, JZ7.8, 0.9 Hz), 7.04 (1H, dd,
JZ7.8, 0.9 Hz), 7.12 (1H, t, JZ7.8 Hz). MS m/z (%) 270
(MC, 100), 241 (22), 225 (40), 209 (28), 197 (38), 169 (32),
155 (40), 131 (23), 99 (34). Calcd for C16H18N2O2: M,
270.1367. Found: m/z 270.1362.
3.1.8. 2-(1,4-Dioxaspiro[4.5]dec-8-ylidenemethyl)-3-
methoxyphenylamine (7h). Colorless oil; IR (neat) 3469
(NH), 3371 (NH), 2949, 2886, 2838, 1615, 1471, 1258,
1210, 1122, 1081, 1034 cmK1; 1H NMR d 1.67 (2H, t, JZ
6.4 Hz), 1.81 (2H, t, JZ6.4 Hz), 2.15 (2H, t, JZ6.4 Hz),
2.49 (2H, t, JZ6.4 Hz), 3.69 (2H, br s), 3.76 (3H, s), 3.97
(4H, m), 5.88 (1H, s), 6.31 (1H, d, JZ8.2 Hz), 6.36 (1H, d,
JZ8.3 Hz), 7.02 (1H, t, JZ8.2 Hz). MS m/z (%) 275 (MC,
100), 230 (26), 213 (16), 189 (34), 174 (40), 160 (24), 136
(63), 130 (10), 117 (8), 106 (15). Calcd for C16H21NO3: M,
275.1520. Found: m/z 275.1520.
3.1.14. 3-Amino-4-(1,4-dioxaspiro[4.5]dec-8-ylidene-
methyl)benzonitrile (7o). Colorless oil; IR (neat) 3475
(NH), 3370 (NH), 2953, 2923, 2874, 2229 (CN), 1627,
1424, 1117, 1083, 1032, 909 cmK1; 1H NMR d 1.67 (2H, t,
JZ6.6 Hz), 1.81 (2H, t, JZ6.6 Hz), 2.31 (2H, t, JZ6.4 Hz),
2.47 (2H, t, JZ6.4 Hz), 3.87 (2H, br s), 3.97–4.00 (4H, m),
6.03 (1H, s), 6.92 (1H, d, JZ1.2 Hz), 6.99 (1H, dd, JZ7.6,
1.2 Hz), 7.03 (1H, d, JZ7.6 Hz). MS m/z (%) 270 (MC,
100), 257 (10), 241 (15), 225 (28), 208 (30), 197 (19), 183
(23), 169 (52), 155 (57), 132 (99), 99 (40), 86 (44). Calcd for
C16H18N2O2: M, 270.1367. Found: m/z 270.1370.
3.1.9. 2-(1,4-Dioxaspiro[4.5]dec-8-ylidenemethyl)-5-
methoxyphenylamine (7i). Colorless crystals; mp 87–
88 8C (AcOEt/hexane); IR (KBr) 3466 (NH), 3363 (NH),
2953, 2901, 1599, 1622, 1578, 1506, 1209, 1081, 1030,
903 cmK1; 1H NMR d 1.66 (2H, t, JZ6.4 Hz), 1.79 (2H, t,
JZ6.6 Hz), 2.35 (2H, t, JZ6.6 Hz), 2.44 (2H, t, JZ6.6 Hz),
3.69 (2H, br s), 3.76 (3H, s), 3.97–3.99 (4H, m), 6.03 (1H,
s), 6.26 (1H, d, JZ2.7 Hz), 6.31 (1H, dd, JZ8.2, 2.7 Hz),
6.88 (1H, d, JZ8.2 Hz). MS m/z (%) 275 (MC, 100), 230
(26), 214 (20), 189 (30), 174 (22), 160 (23), 136 (75), 130
(6), 117 (8). Calcd for C16H21NO3: M, 275.1521. Found: m/z
275.1525. Anal. Calcd for C16H21NO3: C, 69.79; H, 7.69; N,
5.09. Found: C, 69.74; H, 7.54; N, 5.13.
3.1.15. 2-(2-Methylpropenyl)phenylamine (11a). Color-
less oil; IR (neat) 3466 (NH), 3376 (NH), 3022, 2968, 2930,
1
2855, 1615, 1491, 1454, 1299, 750 cmK1; H NMR d 1.71
(3H, s), 1.91 (3H, s), 3.66 (2H, br s), 6.06 (1H, s), 6.69 (1H,
d, JZ7.6 Hz), 6.73 (1H, t, JZ7.6 Hz), 7.00 (1H, d, JZ
7.6 Hz), 7.05 (1H, t, JZ7.6 Hz). MS m/z (%) 147 (MC,
100), 117 (30), 106 (30), 91 (11), 77 (13), 65 (11). Calcd for
C10H13N: M, 147.1047. Found: m/z 147.1049.
3.1.10. 2-(1,4-Dioxaspiro[4.5]dec-8-ylidenemethyl)-3-
methylphenylamine (7j) and 2-(1,4-dioxaspiro[4.5]dec-
8-ylidenemethyl)-5-methylphenylamine (7k). The reac-
tion gave an inseparable mixture of 7j and 7k. Colorless oil;

T. Satoh et al. / Tetrahedron 61 (2005) 10262–10276
10273
3.1.16. 4-Methoxy-2-(2-methylpropenyl)phenylamine
(11b). Colorless oil; IR (neat) 3440 (NH), 3363 (NH),
2929, 2852, 1603, 1497 cmK1; 1H NMR d 1.73 (3H, d, JZ
1.2 Hz), 1.91 (3H, d, JZ1.2 Hz), 3.43 (2H, br s), 3.74 (3H,
s), 6.06 (1H, br s), 6.61 (1H, m), 6.65 (2H, m). MS m/z (%)
177 (MC, 100), 162 (85), 147 (18), 134 (8), 117 (12), 91 (8).
Calcd for C11H15NO: M, 177.1152. Found: m/z 117.1154.
p-tolyl sulfoxide (1.0 g; 5.3 mmol) in dry THF (5 mL) was
added dropwise to a solution of LDA (7.95 mmol) in 20 mL
of THF at K78 8C. The solution was stirred at K78 8C for
10 min, then methyl vinyl ketone (0.648 mL: 7.95 mmol)
was added. The reaction mixture was stirred for 10 min and
the reaction was quenched by satd aq NH4Cl. The whole
was extracted with CHCl3. The organic layer was washed
once with water and dried over MgSO4. The solvent was
evaporated to leave the adducts as colorless crystals. The
adducts were dissolved in a mixture of acetic anhydride
(11.2 mL) and pyridine (21.4 mL). 4-Dimethylaminopyr-
idine (108 mg; 0.88 mmol) was added to the solution and
the reaction mixture was stirred at room temperature for
15 h. The acetic anhydride and pyridine were evaporated
under vacuum and the residue was purified by silica gel
column chromatography to give the acetate (1.21 g; 76%) as
a colorless oil (a mixture of two diastereomers); IR (neat)
2995, 2945, 1739 (CO), 1370, 1239 (COC), 1092, 1065
3.1.17. 3-Methoxy-2-(2-methylpropenyl)phenylamine
(11c). Colorless oil; IR (neat) 3462 (NH), 3376 (NH),
2930, 2852, 1618, 1506, 1294, 1205, 1168, 1030 cmK1; 1H
NMR d 1.59 (3H, s), 1.94 (3H, d, JZ1.3 Hz), 3.71 (2H, br
s), 3.78 (3H, s), 5.91 (1H, br s), 6.32 (1H, d, JZ8.0 Hz),
6.37 (1H, d, JZ8.0 Hz), 7.02 (1H, t, JZ8.0 Hz). MS m/z
(%) 177 (MC, 80), 162 (100), 147 (30), 131 (12), 117 (8),
106 (16), 91 (10), 77 (18), 65 (6). Calcd for C11H15NO: M,
177.1153. Found: m/z 117.1153.
(SO) cmK1
.
3.1.18. 5-Methoxy-2-(2-methylpropenyl)phenylamine
(11d). Colorless oil; IR (neat) 3473 (NH), 3377 (NH),
2932, 2836, 1612, 1468, 1257, 1129, 1092, 1055, 770 cmK1
;
A solution of the acetate (205 mg; 0.68 mmol) in dry THF
(4 mL) was added dropwise to a solution of N-lithio
2-piperidone [1.7 mmol; prepared from n-BuLi (1.7 mmol)
and 2-piperidone (169 mg; 1.7 mmol) in THF (4 mL) at
0 8C] in THF at 25 8C. The mixture was stirred at 25 8C for
30 min. The reaction was quenched by satd aq NH4Cl and
the whole was extracted with CHCl3 and the organic layer
was washed three times with water. The organic layer was
dried over MgSO4. The solvent was evaporated to leave
colorless crystals, which were purified by silica gel column
chromatography to give 13E (79 mg; 48%) and 13Z (79 mg;
48%).
1H NMR d 1.70 (3H, s), 1.89 (3H, s), 3.70 (2H, br s), 3.76
(3H, s), 5.99 (1H, s), 6.26 (1H, d, JZ2.8 Hz), 6.31 (1H, dd,
JZ8.3, 2.8 Hz), 6.90 (1H, d, JZ8.3 Hz). MS m/z (%) 178
(12), 177 (MC, 100), 162 (66), 136 (48), 131 (10), 117 (10),
91 (8). Calcd for C11H15NO: M, 177.1152. Found: m/z
177.1150.
3.1.19. N-Methyl-N-[2-(2-methylpropenyl)phenyl]amine
(11e). Colorless oil; IR (neat) 3429 (NH), 2911, 2814, 1602,
1
1578, 1506, 1459, 748 cmK1; H NMR d 1.69 (3H, d, JZ
0.9 Hz), 1.91 (3H, d, JZ1.3 Hz), 2.85 (3H, s), 3.76 (1H, br
s), 6.00 (1H, br s), 6.61 (1H, d, JZ7.3 Hz), 6.68 (1H, t, JZ
7.3 Hz), 6.98 (1H, d, JZ7.3 Hz), 7.16 (1H, t, JZ7.3 Hz).
MS m/z (%) 161 (MC, 100), 146 (84), 131 (36), 118 (58),
115 (12), 91 (16), 77 (12), 65 (6). Calcd for C11H15N: M,
161.1204. Found: m/z 161.1206.
Compound 13E: Colorless needles; mp 103–104 8C
(AcOEt/hexane); IR (KBr) 3095, 3053, 3024, 2918, 1555,
1494, 1417, 1086, 1059 (SO), 922, 899, 807 cmK1 1H
;
NMR d 2.13 (3H, s), 2.41 (3H, s), 5.50 (1H, d, JZ11.0 Hz),
5.63 (1H, d, JZ16.8 Hz), 7.30 (2H, d, JZ7.9 Hz), 7.47 (1H,
dd, JZ16.8, 11.0 Hz), 7.48 (2H, d, JZ7.9 Hz). MS m/z (%)
240 (MC, 15), 223 (12), 205 (10), 188 (16), 175 (18), 157
(25), 139 (46), 124 (46), 117 (52), 105 (25), 89 (72), 77 (20),
65 (100). Calcd for C12H13ClOS: M, 240.0374. Found: m/z
240.0369. Anal. Calcd for C12H13ClOS: C, 59.87; H, 5.44;
Cl, 14.73; S, 13.32. Found: C, 59.89; H, 5.29; Cl, 14.73; S,
13.09.
3.1.20. 2-(2-Methylpropenyl)naphthalen-1-ylamine
(11f). Colorless oil; IR (neat) 3469 (NH), 3383 (NH),
3054, 2929, 1610, 1565, 1507, 1430, 1400 cmK1; 1H NMR
d 1.72 (3H, s), 1.97 (3H, d, JZ1.2 Hz), 4.20 (2H, br s), 6.25
(1H, s), 7.17 (1H, d, JZ8.3 Hz), 7.27 (1H, d, JZ8.3 Hz),
7.41–7.44 (2H, m), 7.77 (1H, dd, JZ6.6, 2.5 Hz), 7.81–7.83
(1H, m). MS m/z (%) 197 (MC, 100) 182 (85), 167 (30), 156
(22), 90 (6), 28 (24). Calcd for C14H15N: M, 197.1204.
Found: m/z 197.1211.
Compound 13Z: Colorless crystals; mp 77–78 8C (AcOEt/
hexane); IR (KBr) 3050, 3002, 2957, 1564, 1492, 1447,
1
1418, 1087, 1060 (SO), 939, 891, 810 cmK1; H NMR d
3.1.21. 2-(2-Methylpropenyl)anthracen-1-ylamine (11g).
Colorless crystals; mp 98–100 8C (hexane); IR (KBr) 3469
(NH), 3383 (NH), 3050, 2960, 2926, 1617, 1527, 1402,
2.40 (3H, s), 2.41 (3H, s), 5.56 (1H, d, JZ11.0 Hz), 5.69
(1H, d, JZ17.4 Hz), 6.93 (1H, dd, JZ17.4, 11.0 Hz), 7.31
(2H, d, JZ8.3 Hz), 7.49 (2H, d, JZ8.3 Hz). MS m/z (%)
240 (MC, 20), 223 (22), 192 (15), 187 (15), 177 (22), 157
(65), 139 (45), 123 (55), 105 (30), 91 (40), 77 (20), 65 (100).
Calcd for C12H13ClOS: M, 240.0374. Found: m/z 240.0371.
Anal. Calcd for C12H13ClOS: C, 59.87; H, 5.44; Cl, 14.73;
S, 13.32. Found: C, 59.92; H, 5.21; Cl, 14.62; S, 13.08.
1
1387, 891, 873, 735 cmK1; H NMR d 1.75 (3H, s), 2.00
(3H, d, JZ1.2 Hz), 4.34 (2H, br s), 6.30 (1H, s), 7.19 (1H, d,
JZ8.5 Hz), 7.41–7.46 (3H, m), 7.95–7.97 (1H, m), 7.99
(1H, m), 8.34 (1H, s), 8.39 (1H, s). MS m/z (%) 247 (MC,
100), 232 (26), 217 (20), 202 (6), 115 (8), 28 (24). Calcd for
C18H17N: M, 247.1360. Found: m/z 247.1370. Anal. Calcd
for C18H17N: C, 87.41; H, 6.93; N, 5.66. Found: C, 87.69; H,
6.87; N, 5.57.
3.1.23. (E)-1-Chloro-2-methyl-1-(p-tolylsulfinyl)-1-hep-
tene (14E) and (Z)-1-chloro-2-methyl-1-(p-tolylsulfinyl)-
1-heptene (14Z). These compounds were synthesized from
chloromethyl p-tolyl sulfoxide and 2-heptanone in a similar
way as described above. The acetates were isolated by silica
3.1.22. (E)-1-Chloro-2-methyl-1-(p-tolylsulfinyl)-1,3-
butadiene (13E) and (Z)-1-chloro-2-methyl-1-(p-tolylsul-
finyl)-1,3-butadiene (13Z). A solution of chloromethyl

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gel column chromatography to give more polar acetate-P
(55%) as a colorless oil and less polar acetate-L (39%) as
colorless crystals.
JZ6.3, 1.5 Hz), 3.69 (2H, br s), 5.88–5.91 (1H, m), 6.10
(1H, s), 6.25 (1H, d, JZ10.0 Hz), 6.69 (1H, d, JZ8.0 Hz),
6.74 (1H, t, JZ7.5 Hz), 7.04–7.07 (2H, m). MS m/z (%) 185
(MC, 100), 170 (13), 157 (63), 143 (13), 130 (33), 115 (10),
106 (52), 91 (12), 77 (12). Calcd for C13H15N: M, 185.1204.
Found: m/z 185.1212.
Acetate-P; IR (neat) 2956, 2870, 1732 (CO), 1494, 1461,
1369, 1243 (COC), 1154, 1093, 1066 (SO), 1018, 820,
1
516 cmK1; H NMR d 0.89 (3H, t, JZ7.0 Hz), 1.20–1.43
(6H, m), 1.71 (3H, s), 1.87–1.93 (1H, m), 2.14 (3H, s), 2.17–
2.20 (1H, m), 2.42 (3H, s), 5.25 (1H, s), 7.33 (2H, d, JZ
8.3 Hz), 7.47 (2H, d, JZ8.3 Hz). MS m/z (%) 344 (MC, 2),
205 (32), 140 (87), 139 (36), 109 (26), 91 (16), 65 (6), 43
(100). Calcd for C17H25ClO3S: M, 344.1213. Found: m/z
344.1216.
3.1.26. (Z)-2-(Cyclohex-2-enylidenemethyl)naphthalen-
1-ylamine (17Z). Colorless crystals; mp 71–73 8C (hexane);
IR (KBr) 3478 (NH), 3392 (NH), 2928, 2856, 2822, 1614,
1
1403, 790, 736 cmK1; H NMR d 1.84 (2H, quintet, JZ
6.2 Hz), 2.20–2.21 (2H, m), 2.53 (2H, t, JZ6.3 Hz), 4.16
(2H, br s), 5.88–5.91 (1H, m), 6.18 (1H, s), 6.32 (1H, dd, JZ
10.0, 0.9 Hz), 7.23 (1H, d, JZ8.3 Hz), 7.26 (1H, d, JZ
8.3 Hz), 7.40–7.43 (2H, m), 7.74–7.76 (1H, m), 7.78–7.80
(1H, m). MS m/z (%) 235 (MC, 100), 220 (10), 207 (42),
193 (8), 180 (30), 167 (6), 156 (18), 143 (6). Calcd for
C17H17N: M, 235.1359. Found: m/z 235.1353.
Acetate-L: Colorless crystals; mp 64–65 8C (AcOEt/
hexane); IR (KBr) 2950, 2931, 1726 (CO), 1242 (COC),
1
1087, 1463 (SO), 515 cmK1; H NMR d 0.92 (3H, t, JZ
7.0 Hz), 1.33–1.48 (6H, m), 1.61 (3H, s), 1.99–2.06 (1H, m),
2.09 (3H, s), 2.35–2.40 (1H, m), 2.42 (3H, s), 5.38 (1H, s),
7.33 (2H, d, JZ8.0 Hz), 7.47 (2H, d, JZ8.0 Hz). MS m/z
(%) 344 (MC, 2), 205 (32), 140 (50), 139 (33), 109 (25), 91
(15), 65 (6), 43 (100). Calcd for C17H25ClO3S: M, 344.1231.
Found: m/z 344.1233. Anal. Calcd for C17H25ClO3S: C,
59.20; H, 7.31; Cl, 10.28; S, 9.3. Found: C, 59.18; H, 7.36;
Cl, 10.15; S, 9.23.
3.1.27. (E)-2-(Cyclohex-2-enylidenemethyl)naphthalen-
1-ylamine (17E). Colorless oil; IR (neat) 3472 (NH),
3385 (NH), 3054, 3021, 2930, 2862, 2829, 1615, 1403, 806,
1
758, 737 cmK1; H NMR d 1.68 (2H, quintet, JZ6.2 Hz),
2.17–2.20 (2H, m), 2.46 (2H, t, JZ6.2 Hz), 4.18 (2H, br s),
5.90–5.93 (1H, m), 6.29 (1H, s), 6.31 (1H, d, JZ10.1 Hz),
7.22 (1H, d, JZ8.6 Hz), 7.26 (1H, d, JZ8.6 Hz), 7.39–7.43
(2H, m), 7.74–7.76 (1H, m), 7.79–7.80 (1H, m). MS m/z (%)
235 (MC, 100), 220 (10), 207 (44), 193 (8), 180 (30), 167
(8), 156 (18), 143 (6). Calcd for C17H17N: M, 235.1360.
Found: m/z 235.1366.
Treatment of the acetate-L and acetate-P with N-lithio
2-piperidone in THF at 25 8C gave 14Z (93%) and 14E
(96%), respectively.
Compound 14E: Colorless oil; IR (neat) 2957, 2929, 2860,
1
1493, 1456, 1088, 1061 (SO), 808 cmK1; H NMR d 0.87
3.1.28. (Z)-2-(Cyclohex-2-enylidenemethyl)athracen-1-
ylamine (18Z). Colorless amorphous; IR (KBr) 3456
(3H, t, JZ7.0 Hz), 1.26–1.31 (4H, m), 1.45–1.50 (2H, m),
2.31 (3H, s), 2.33 (2H, t, JZ8.0 Hz), 2.41 (3H, s), 7.30 (2H,
d, JZ7.9 Hz), 7.46 (2H, d, JZ7.9 Hz). MS m/z (%) 284
(MC, 26), 267 (100), 211 (24), 175 (32), 140 (36), 139 (26),
123 (21), 91 (36), 89 (17), 65 (17). Calcd for C15H21ClO3S:
M, 284.1002. Found: m/z 284.0994.
1
(NH), 3382 (NH), 2929, 2858, 1618, 875, 738 cmK1; H
NMR d 1.85 (2H, quintet, JZ6.2 Hz), 2.21–2.23 (2H, m),
2.55 (2H, t, JZ5.9 Hz), 4.34 (2H, br s), 5.91–5.94 (1H, m),
6.22 (1H, s), 6.37 (1H, dd, JZ10.0, 0.9 Hz), 7.24 (1H, dd,
JZ8.7, 1.9 Hz), 7.40–7.43 (3H, m), 7.93–7.97 (2H, m), 8.31
(1H, s), 8.34 (1H, s). MS m/z (%) 285 (MC, 100), 257 (16),
230 (16), 206 (10), 193 (6). Calcd for C21H19N: M,
285.1516. Found: m/z 285.1509.
Compound 14Z: Colorless oil; IR (neat) 2957, 2929, 2861,
1
1493, 1456, 1088, 1062 (SO), 808 cmK1; H NMR d 0.94
(3H, t, JZ6.6 Hz), 1.38–1.41 (4H, m), 1.50–1.59 (2H, m),
2.00 (3H, s), 2.41 (3H, s), 2.73 (2H, t, JZ7.9 Hz), 7.31 (2H,
d, JZ7.9 Hz), 7.49 (2H, d, JZ8.2 Hz). MS m/z (%) 284
(MC, 85), 267 (100), 211 (75), 175 (56), 140 (90), 139 (63),
123 (56), 91 (72), 89 (68), 55 (42), 41 (42). Calcd for
C15H21ClOS: M, 284.1001. Found: m/z 284.0993.
3.1.29. (E)-2-(Cyclohex-2-enylidenemethyl)athracen-1-
ylamine (18E). Colorless crystals; mp 114–115 8C
(hexane); IR (KBr) 3462 (NH), 3389 (NH), 2928, 2827,
1
1613, 869, 737 cmK1; H NMR d 1.71 (2H, quintet, JZ
6.1 Hz), 2.19–2.21 (2H, m), 2.49 (2H, t, JZ6.0 Hz), 4.35
(2H, br s), 5.91–5.95 (1H, m), 6.33–6.34 (2H, m), 7.24 (1H,
d, JZ8.5 Hz), 7.41–7.43 (3H, m), 7.93–7.97 (2H, m), 8.31
(1H, m), 8.35 (1H, s). MS m/z (%) 285 (MC, 100), 256 (18),
230 (18), 206 (10). Calcd for C21H19N: M, 285.1517. Found:
m/z 285.1521. Anal. Calcd for C21H19N: C, 88.38; H, 6.71;
N, 4.91. Found: C, 87.79; H, 6.44; N, 4.86.
3.1.24. (Z)-2-(Cyclohex-2-enylidenemethyl)phenylamine
(16Z). Colorless oil; IR (neat) 3467 (NH), 3376 (NH), 3030,
1
2932, 2829, 1615, 1489, 1453, 747 cmK1; H NMR d 1.81
(2H, quintet, JZ6.2 Hz), 2.18–2.20 (2H, m), 2.48 (2H, t,
JZ6.0 Hz), 3.69 (2H, br s), 5.87–5.91 (1H, m), 6.01 (1H, s),
6.35 (1H, d, JZ10.8 Hz), 6.69 (1H, d, JZ7.6 Hz), 6.73 (1H,
t, JZ7.3 Hz), 7.04–7.07 (2H, m). MS m/z (%) 185 (MC,
100), 170 (15), 157 (64), 143 (14), 130 (34), 115 (10), 106
(52), 91 (13), 77 (14). Calcd for C13H15N: M, 185.1204.
Found: m/z 185.1210.
3.1.30. (Z)-2-(2-Methylbuta-1,3-dienyl)naphthalen-1-yl-
amine (19Z). Colorless crystals; mp 51–52 8C (hexane); IR
(KBr) 3476 (NH), 3391 (NH), 3055, 2979, 2930, 1618,
1
1404, 900, 810, 762, 738 cmK1; H NMR d 2.07 (3H, s),
4.21 (2H, br s), 5.14 (1H, d, JZ10.7 Hz), 5.36 (1H, d, JZ
17.4), 6.47 (1H, s), 6.65 (1H, dd, JZ17.4, 10.7 Hz), 7.19
(1H, d, JZ8.3 Hz), 7.26 (1H, d, JZ8.3 Hz), 7.41–7.45 (2H,
m), 7.75–7.77 (1H, m), 7.79–7.81 (1H, m). MS m/z (%) 209
(MC, 100), 194 (84), 178 (20), 165 (12), 152 (8), 139 (6), 96
3.1.25. (E)-2-(Cyclohex-2-enylidenemethyl)phenylamine
(16E). Colorless oil; IR (neat) 3461 (NH), 3375 (NH), 3021,
2931, 2862, 2829, 1615, 1489, 1454 cmK1; 1H NMR d 1.68
(2H, quintet, JZ6.2 Hz), 2.16–2.19 (2H, m), 2.47 (2H, dt,

T. Satoh et al. / Tetrahedron 61 (2005) 10262–10276
10275
(12). Calcd for C15H15N: M, 209.1204. Found: m/z
209.1207. Anal. Calcd for C15H15N: C, 86.08; H, 7.22; N,
6.69. Found: C, 85.85; H, 7.24; N, 6.69.
After 10 min, i-PrMgCl (0.84 mmol) was added dropwise
to the reaction mixture at K78 8C to give the magnesium
alkylidene carbenoid. After 5 min, the reaction was
quenched by satd aq NH4Cl and the whole was extract
with CHCl3. The organic layer was washed once with water
and dried over MgSO4. After removal of the solvent, the
product was purified by silica gel column chromatography
to give 19.7 mg (51%) of 22E as a colorless oil; IR (neat)
3.1.31. (E)-2-(2-Methylbuta-1,3-dienyl)naphthalen-1-
ylamine (19E). Colorless oil; IR (neat) 3474 (NH), 3388
(NH), 3055, 2918, 1615, 1403, 902, 797, 760, 737 cmK1; 1H
NMR d 1.89 (3H, s), 4.22 (2H, br s), 5.16 (1H, d, JZ
10.7 Hz), 5.33 (1H, d, JZ17.4 Hz), 6.55 (1H, s), 6.66 (1H,
dd, JZ17.4, 10.7 Hz), 7.21 (1H, d, JZ8.2 Hz), 7.28 (1H, d,
JZ8.2 Hz), 7.42–7.46 (2H, m), 7.77–7.78 (1H, m), 7.81–
7.83 (1H, m). MS m/z (%) 209 (MC, 100), 194 (88), 178
(20), 165 (14), 152 (10), 139 (6), 115 (6), 96 (14). Calcd for
C15H15N: M, 209.1203. Found: m/z 209.1203.
1
2941, 2867, 2834, 1694, 835, 795, 755 cmK1; H NMR d
1.71 (2H, quintet, JZ6.3 Hz), 2.11–2.15 (2H, m), 2.46 (2H,
dt, JZ6.3, 2.1 Hz), 5.83–5.87 (1H, m), 5.91 (1H, s), 6.06
(1H, dt, JZ10.1, 2.0 Hz). MS m/z (%) 128 (MC, 40), 113
(6), 93 (100), 79 (82), 77 (66). Calcd for C7H9Cl: M,
128.0393. Found: m/z 128.0390.
3.1.32. (Z)-2-(2-Methylhept-1-enyl)naphthalen-1-yl-
amine (20Z). Colorless oil; IR (neat) 3467 (NH), 3386
(NH), 2927, 2857, 1611, 1400, 1380 cmK1; 1H NMR d 0.81
(3H, t, JZ6.9 Hz), 1.13–1.23 (4H, m), 1.42 (2H, quintet,
JZ7.6 Hz), 1.94 (3H, s), 2.07 (2H, t, JZ7.8 Hz), 4.17 (2H,
br s), 6.23 (1H, s), 7.14 (1H, d, JZ8.3 Hz), 7.26 (1H, d, JZ
9.2 Hz), 7.40–7.45 (2H, m), 7.76 (1H, m), 7.81 (1H, d, JZ
7.3 Hz). MS m/z (%) 253 (MC, 100), 196 (50), 182 (54), 167
(12), 156 (23), 143 (23). Calcd for C18H23N: M, 253.1828.
Found: m/z 253.1822.
3.1.37. (Z)-3-Cholromethylenecyclohexene (22Z). Color-
less oil; IR (neat) 2940, 2866, 2832, 818, 758, 731 cmK1; 1H
NMR d 1.70–1.75 (2H, m), 2.16–2.20 (2H, m), 2.30–2.33
(2H, m), 5.72 (1H, s), 6.01–6.05 (1H, m), 6.55–6.58 (1H,
m). MS m/z (%) 128 (MC, 32) 113 (9), 93 (67), 83 (100), 79
(47), 77 (46). Calcd for C7H9Cl: M, 128.0393. Found: m/z
128.0391.
3.1.38. (E)-(2-Chloro-1-methylvinyl)benzene (23E).
Colorless oil; IR (neat) 3080, 3059, 2923, 1494, 1443,
1
801, 749, 695 cmK1; H NMR d 2.20 (3H, d, JZ1.2 Hz),
3.1.33. (E)-2-(2-Methylhept-1-enyl)naphthalen-1-yl-
amine (20E). Colorless oil; IR (neat) 3472 (NH), 3384
6.32 (1H, q, JZ1.4 Hz), 7.27–7.31 (1H, m), 7.32–7.34 (4H,
m). MS m/z (%) 152 (MC, 100), 115 (56), 103 (33), 91 (47),
78 (42). Calcd for C9H9Cl: M, 152.0393. Found: m/z
152.0397.
1
(NH), 2928, 2856, 1615, 1403, 800, 760, 734 cmK1; H
NMR d 0.94 (3H, t, JZ6.4 Hz), 1.38 (4H, m), 1.57 (2H, t,
JZ6.7 Hz), 1.69 (3H, s), 2.24 (2H, t, JZ7.5 Hz), 4.18 (2H,
br s), 6.25 (1H, s), 7.17 (1H, d, JZ8.3 Hz), 7.27 (1H, d, JZ
8.3 Hz), 7.40–7.45 (2H, m), 7.76 (1H, d, JZ8.0 Hz), 7.81
(1H, d, JZ7.7 Hz). MS m/z (%) 253 (MC, 100), 238 (6),
196 (53), 182 (61), 167 (13), 156 (25), 143 (23). Calcd for
C18H23N: M, 253.1829. Found: m/z 253.1837.
3.1.39. (Z)-(2-Chloro-1-methylvinyl)benzene (23Z).
Colorless oil; IR (neat) 3059, 2970, 2916, 1494, 1442,
1
835, 762, 697 cmK1; H NMR d 2.09 (3H, d, JZ1.5 Hz),
6.11 (1H, q, JZ1.5 Hz), 7.28–7.32 (1H, m), 7.37–7.38 (4H,
m). MS m/z (%) 152 (MC, 100) 115 (56), 103 (33), 91 (18),
78 (43). Calcd for C9H9Cl: M, 152.0393. Found: m/z
152.0390.
3.1.34. (Z)-2-(2-Phenylpropenyl)naphthalen-1-ylamine
(21Z). Colorless crystals; mp 110–112 8C (AcOEt/hexane);
IR (KBr) 3487 (NH), 3391 (NH), 2965, 2926, 2869, 1614,
1
1406, 804, 760, 748, 696 cmK1; H NMR d 2.32 (3H, s),
Acknowledgements
4.24 (2H, br s), 6.55 (1H, s), 6.86 (1H, d, JZ8.6 Hz), 7.02
(1H, d, JZ8.6 Hz), 7.13–7.20 (5H, m), 7.36–7.42 (2H, m),
7.65–7.67 (1H, m), 7.76 (1H, d, JZ8.0 Hz). MS m/z (%)
259 (MC, 92), 244 (100), 215 (8), 182 (11), 167 (10), 156
(18), 121 (12). Calcd for C19H17N: M, 259.1359. Found: m/z
259.1355. Anal. Calcd for C19H17N: C, 87.99; H, 6.61; N,
5.40. Found: C, 87.82; H, 6.58; N, 5.48.
This work was supported by a grant from the Ministry
of Education, Culture, Sports, Science and Technology of
Japan to promote multi-disciplinary research project, which
is gratefully acknowledged.
3.1.35. (E)-2-(2-Phenylpropenyl)naphthalen-1-ylamine
(21E). Colorless amorphous; IR (KBr) 3484 (NH), 3399
References and notes
(NH), 3049, 2919, 2851, 1608, 1404, 761, 740, 697 cmK1
;
1H NMR d 2.16 (3H, s), 4.27 (2H, br s), 6.90 (1H, s), 7.28
(1H, d, JZ8.3 Hz), 7.32–7.34 (2H, m), 7.40 (2H, t, JZ
7.6 Hz), 7.44–7.48 (2H, m), 7.61 (2H, d, JZ8.0 Hz), 7.79–
7.81 (1H, m), 7.84–7.86 (1H, m). MS m/z (%) 259 (MC, 92),
244 (100), 215 (8), 182 (11), 167 (8), 156 (17), 122 (8), 121
(9). Calcd for C19H17N: M, 259.1360. Found: m/z 259.1364.
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