DTBB-catalysed lithiation of acenaphthylene and reaction with carbonyl compounds

Article abstract of DOI:10.1055/s-2008-1042943

The reaction of acenaphthylene with an excess of lithium powder and a catalytic amount of DTBB (7.5 mol%) in tetrahydrofuran at -70°C followed by treatment with a carbonyl compound [Me₂CO, Et₂CO, i-Pr₂CO, (c-C₃H₅)₂CO, cyclopentanone, cyclohexanone, 2-adamantanone, Ph₂CO, t-BuCHO] leads, after hydrolysis with water, to an easily chromatographically separable mixture of two products resulting from disubstitution at the 1,2-positions and monosubstitution at the 1-position, respectively. The reaction is regio- and stereoselective, so in the case of the disubstituted compounds only the trans-diastereomers are obtained. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2008-1042943

PAPER
1241
DTBB-Catalysed Lithiation of Acenaphthylene and Reaction with Carbonyl
Compounds
L
ithiationandFur
i
R
e
c
action of
A
t
cenaph
othylene r J. Lillo, Cecilia Gómez,* Miguel Yus*
Departamento de Química Orgánica, Facultad de Ciencias and Instituto de Síntesis Orgánica (ISO), Universidad de Alicante,
Apdo. 99, 03080 Alicante, Spain
Fax +34(965)903549; E-mail: cgomez@ua.es; E-mail: yus@ua.es
Received 27 December 2007; revised 11 January 2008
Dedicated to the memory of Professor Lorenzo Pueyo
putationally, we have proven that under adequate reaction
Abstract: The reaction of acenaphthylene with an excess of lithium
conditions (excess of the metal) dianionic species are gen-
powder and a catalytic amount of DTBB (7.5 mol%) in tetrahydro-
furan at –70 °C followed by treatment with a carbonyl compound
[Me2CO, Et2CO, i-Pr2CO, (c-C3H5)2CO, cyclopentanone, cyclohex-
erated from an arene and lithium powder, and that these
species show a special reactivity.7
anone, 2-adamantanone, Ph2CO, t-BuCHO] leads, after hydrolysis
with water, to an easily chromatographically separable mixture of
cess of sodium gives the expected dianion 2, which is pro-
two products resulting from disubstitution at the 1,2-positions and
Concerning acenaphthylene (1), its reaction with an ex-
tonated first at the 5-position,8a reacting then with a
monosubstitution at the 1-position, respectively. The reaction is
reactive alkyl halide at the 1-position to give dehy-
droacenaphthylene derivatives of type 3, contaminated
with considerable amounts of acenaphthene (4) and the
corresponding 1,1-disubstituted products of type 5
(Figure 1).8b The use of other metals, such as magne-
sium,9a calcium9b or ytterbium,9b allows the introduction
of two silicon moieties at the 1,2-positions, whereas met-
alation of compounds 1 or 4 with diisobutylaluminium
hydride10a or n-butyllithium,10b respectively, allows the
introduction of electrophilic fragments at the 1-, 3- or 5-
position, depending on the reaction conditions.11
regio- and stereoselective, so in the case of the disubstituted com-
pounds only the trans-diastereomers are obtained.
Key words: DTBB-catalysed lithiation, acenaphthylene, 1,2-diols,
dianionic species
In aromatic compounds, the generation of anionic species
frequently occurs by the addition of one or two electrons
to the LUMO of the starting arene, consequently disturb-
ing the aromatic character, resulting in negatively charged
intermediates able to react with electrophiles to initially
give non-aromatic compounds. These molecules tend to
aromatise mainly by oxidation, in many cases spontane-
ously in air, or by any suitable reagent present in the reac-
tion mixture. Especially for dianionic species, the
possibility of introducing two electrophilic fragments in
only one reaction step opens the way for achieving difunc-
tionalised compounds through a very simple tandem pro-
cess.
2–
1
2
3
4
8
7
5
6
1
2
R
R
R
In the last few years we have been investigating the gen-
eration, reactivity and applications of different dianionic
species in synthetic organic chemistry, especially those
derived from naphthalene and 4,4¢-di-tert-butylbiphenyl
(DTBB). Actually, it has been shown that these two are-
nes are adequate catalysts in many lithiation processes,1
which have been used by our group to perform new reac-
tions unable to be done using other methodologies.
Among them, this arene-catalysed lithiation has been used
mainly to prepare organolithium compounds from non-
halogenated materials (of type RX)2 or heterocycles,3 to
generate very unstable functionalised organolithium inter-
mediates,4 to produce dilithiated synthons,5 and to acti-
vate other metals to give very reactive metallic
nanoparticles.6 In addition, either experimentally or com-
3
4
5
Figure 1
In this paper we report the lithiation of acenaphthylene12
and the further reaction with carbonyl compounds in order
to prepare mainly trans-1,2-disubstituted derivatives,
which are in almost all cases contaminated with variable
amounts of the corresponding compounds monosubsti-
tuted at the 1-position.
The reaction of commercially available acenaphthylene
(1) with an excess of lithium powder (1:7 molar ratio) and
a catalytic amount of DTBB (7.5 mol%) in tetrahydrofu-
ran for two hours at –70 °C led to a suspension which, af-
ter filtration at the same temperature in order to remove
the excess lithium, was treated with a carbonyl compound
SYNTHESIS 2008, No. 8, pp 1241–1248
x
x
.
x
x
.2
0
0
8
Advanced online publication: 18.03.2008
DOI: 10.1055/s-2008-1042943; Art ID: Z29507SS
© Georg Thieme Verlag Stuttgart · New York

1242
V. J. Lillo et al.
PAPER
(1:2.2 molar ratio) at –70 to –30 °C for one hour giving, (1) Since acenaphthylene itself can act as an electron-
after final hydrolysis with water, a mixture of compounds carrier agent,7h the reaction can also be performed in the
6 and 7, the former normally being the main product absence of DTBB, which results in slightly lower yields in
(Scheme 1 and Table 1). The reaction products were eas- general, a lower proportion of the disubstituted compound
ily separated and purified by column chromatography, the 6 and the crude reaction mixture being less clean. Table 2
rest of the reaction mixture being the corresponding re- shows the results obtained under comparable reaction
duced material 4, also very easily removed chromato- conditions.
graphically from products 6 and 7.
Table 2 Comparison of the Results in the Lithiation of Acenaph-
thylene with or without DTBB
OH
OH
HO
R1
R1
R2
R1
R2
With DTBB
Without DTBB
R2
Electrophile
Yielda (%) Yielda (%) Yielda (%) Yielda (%)
i–iii
+
of 6
48
of 7
38
of 6
40
of 7
47
Et2CO
1
6
7
i-Pr2CO
47
37
37
45
Scheme 1 Reagents and conditions: (i) excess Li (7 equiv), DTBB
(7.5 mol%), THF, –70 °C, 2 h, then filtration; (ii) R1R2CO [Me2CO,
Et2CO, i-Pr2CO, (c-C3H5)2CO, cyclopentanone, cyclohexanone, 2-
adamantanone, Ph2CO, t-BuCHO] (2.2 equiv), –70 to –30 °C, 1 h;
(iii) H2O, –30 °C to r.t., 1 h.
a GLC yields determined from the crude reaction mixture.
(2) When the reaction was performed under Barbier-type
reaction conditions (lithiation in the presence of the elec-
trophile)13 the yields were lower than when working with
a two-step process (Grignard-type conditions), except in
the case of cyclohexanone as electrophile (Table 1, entry
6).
Table 1 Preparation of Compounds 6 and 7
Entry
R1
R2
Product
6, 7
Yielda
(%)
Ratiob
6/7
(3) Normally, the best results were obtained when the ex-
cess lithium was filtered off before the reaction with the
electrophile, except for dicyclopropyl ketone; in this case,
the reaction under the general conditions gave a 56% yield
of the diol 6d, whereas without removal of the excess lith-
ium powder a 68% yield of the same diol was obtained
(Table 1, entry 4). However, upon filtering off the excess
lithium powder, no formation of compound 7 was ob-
served.
1
Me
Me
a
b
c
d
e
f
77
84
78
78
64
60
1:3.5
1.2:1
1.2:1
6.8:1
1:12
2
Et
Et
3
i-Pr
i-Pr
c-C3H5
4c
5
c-C3H5
(CH2)4
(CH2)5
6d
1:1.1
(4) For 2-adamantanone and benzophenone14 (Table 1,
entries 7 and 8), the diol of type 6 was the only reaction
product isolated, without any contamination by the mono-
substituted product of type 7. In contrast, in the case of cy-
clopentanone (Table 1, entry 5), the expected diol 6e was
obtained in a very poor yield (ca. 5%).
7
g
77e
1:0
8
9
Ph
Ph
H
h
i
72e
83f
1:0
t-Bu
4.9:1
(5) As expected, the use of pivalaldehyde as electrophile
gave a mixture of three diastereomers of diol 6i, which
could be separated by column chromatography; however,
in the case of 7i only one diastereomer was obtained
(Table 1, entry 9 and footnote f).
a Isolated yield after column chromatography (silica gel, hexane–
EtOAc), based on the starting material 1.
b Determined after the separation of pure compounds 6 and 7.
c This reaction was performed without filtering off the excess lithium
powder.
d This reaction was carried out in the presence of the electrophile
(Barbier conditions, see reference 13).
(6) When chlorotrimethylsilane was used as electrophile
under different reaction conditions, an intractable mixture
of mono- and polysilylated products was obtained; in any
case, the corresponding disubstituted product was ob-
tained in less than 10% yield.
e Isolated yield after recrystallisation from hexane–EtOAc, based on
the starting material 1.
f For compound 6i three diastereomers (38, 21 and 10% isolated
yields) were separated and isolated by column chromatography (silica
gel, hexane–EtOAc) in pure form (>90% from GLC and/or 300 MHz
1H NMR data). For compound 7i only one diastereomer was isolated
by column chromatography.
(7) Finally, deuteration of the lithiation mixture with deu-
terium oxide gave the corresponding dideuterated product
in 92% (GLC/MS) yield as a mixture of different regio-
isomers, as could be expected from the literature data.8
Some remarks about the reaction shown in Scheme 1 fol-
low:
In all cases, diols 6 were characterised as the shown trans-
diastereomers, which in the case of compounds 6c, 6d, 6f
Synthesis 2008, No. 8, 1241–1248 © Thieme Stuttgart · New York

PAPER
Lithiation and Further Reaction of Acenaphthylene
1243
Figure 2 X-ray crystal structures of compounds 6c, 6d, 6f and 6h
–
and 6h gave crystals suitable for analysis by X-ray dif-
fractometry.15 The corresponding results are summarised
in Figure 2.
E
E
E
Li
Li
Concerning a possible reaction mechanism, in the pres-
ence of an excess of lithium, the starting acenaphthylene
(1) is converted into the dianion 2 (see above), which is
trapped by a molecule of the electrophile to give the
monosubstituted anion of type 8 (E = R1R2COLi). Before
reaction with the first molecule of the electrophile, the di-
anion 2 which is rather unstable can also abstract a proton
from the reaction medium (probably from THF)16 giving
a monoanion of type 8 with E = H. In a second step, inter-
mediates 8 prefer to react regioselectively at the 2-posi-
tion with a second molecule of the carbonyl compound to
yield a dialkoxide (E = R1R2COLi), or a monoalkoxide
(E, E = H, R1R2COLi) of type 9, which are the precursors
of the final products 6 and 7, respectively. Of course,
some of the monosubstituted intermediate 8 with E = H
can also abstract a second proton during the second step
of the reaction, or during the workup, to give the dihydro
product 4 (9 with E = H), that we always observed in
small amounts as a byproduct (Figure 3).
10
8
9
Figure 3
acenaphthene (4) by direct lithiation of acenaphthylene
(1) using a DTBB-catalysed lithiation. The reaction is not
only regio- but also stereoselective giving only the trans-
diols 6, contaminated with variable amounts of the corre-
sponding monosubstituted derivatives 7. Both types of
compounds are easily separated from the mixture of reac-
tion products by simple column chromatography. It is
worthy to note that previous studies on metalation of the
starting material 1 never gave 1,2-disubstitution, except
for the reaction with chlorosilanes.17
All commercially available reagents (Acros, Aldrich, Fluka) were
used without further purification, except for acenaphthylene
(Aldrich, purity 75%) which was purified by treatment with DDQ
and filtration through silica gel. Melting points were obtained with
a Reichert Thermovar apparatus. 1H and 13C NMR spectra were re-
corded on Bruker AC-300 and AC-400 spectrometers in CDCl3 so-
In conclusion, we report here a simple methodology for
the synthon 10, which allows the introduction of two sep-
arate electrophilic fragments at the 1,2-positions of
Synthesis 2008, No. 8, 1241–1248 © Thieme Stuttgart · New York

1244
V. J. Lillo et al.
PAPER
lution. Chemical shifts (d) are reported in ppm relative to TMS. MS
were recorded on a Hewlett-Packard HP 6890 mass spectrometer
with an Agilent 5973 Network mass selective detector operating at
an ionization potential of 70 eV. HRMS (EI) were performed on a
Finnigan MAT 95S apparatus by the Technical Services of the Uni-
versity of Alicante. The X-ray diffraction analyses were carried out
by the Technical Services of the University of Alicante on a Bruker
CCD-Apex instrument equipped with an X-ray tube with a Mo an-
ode and Kryoflex® low-temperature equipment. Elemental analyses
were performed by the Microanalyses Service at the University of
Alicante. Retention times (tR) were obtained with an Agilent Tech-
nologies 6890N instrument equipped with a flame ionization detec-
tor and a 30 m HP-5 capillary column (0.32 mm diameter, 0.25 mm
2-(1,2-Dihydroacenaphthylen-1-yl)propan-2-ol (7a)10a
Yellow oil; yield: 60%; tR = 14.9 min; Rf = 0.31 (hexane–EtOAc,
8:2).
IR (film): 3404 (OH), 3047 (=CH) cm–1.
1H NMR (300 MHz): d = 1.13 (s, 3 H, CH3), 1.31 (s, 3 H, CH3), 1.63
(s, 1 H, OH), 3.21–3.29 (dd, J = 17.6, 3.4 Hz, 1 H, CHCOH), 3.44–
3.54 (dd, J = 8.4, 3.4 Hz, 1 H, CHH), 3.75–3.80 (dd, J = 17.6, 8.4
Hz, 1 H, CHH), 7.24–7.28 (m, 1 H, ArH), 7.41–7.51 (m, 3 H, 3 ×
ArH), 7.58–7.66 (m, 2 H, 2 × ArH).
13C NMR (75 MHz): d = 25.9, 28.1 (CH3), 34.5 (CH2), 54.9 (CH),
73.7 (COH), 119.0, 121.2, 122.3, 123.3, 127.6, 127.7 (ArCH),
131.4, 139.6, 144.2, 145.6 (ArC).
film thickness), using nitrogen (2 mL/min) as carrier gas, Tinjector
=
MS: m/z (%) = 212 (8) [M+], 155 (13), 154 (100), 153 (69), 152
(38), 151 (11), 59 (14).
275 °C, Tdetector = 300 °C, Tcolumn = 60 °C (3 min) and 60–270 °C
(15 °C/min), P = 40 kPa.
HRMS: m/z calcd for C15H16O: 212.1201; found: 212.1205.
Alcohols 6 and 7 by the DTBB-Catalysed Lithiation of
Acenaphthylene (1) and Subsequent Reaction with Carbonyl
Compounds; General Procedure
trans-3,3¢-(1,2-Dihydroacenaphthylene-1,2-diyl)dipentan-3-ol
(6b)
Yellow solid; yield: 46%; mp 120 °C (hexane–EtOAc); tR = 19.1
min; Rf = 0.15 (hexane–EtOAc, 8:2).
IR (KBr): 3384 (OH), 3044 (=CH) cm–1.
1H NMR (400 MHz): d = 0.57 (t, J = 7.5 Hz, 6 H, 2 × CH3), 0.73–
0.90 (m, 2 H, CH2), 1.19–1.70 (m, 2 H, CH2), 1.22 (t, J = 7.5 Hz, 6
H, 2 × CH3), 1.83–1.89 (m, 4 H, 2 × CH2), 2.79 (s, 2 H, 2 × OH),
4.17 (s, 2 H, 2 × CH), 7.29 (d, J = 6.9 Hz, 2 H, 2 × ArH), 7.43–7.47
(m, 2 H, 2 × ArH), 7.64 (d, J = 8.2 Hz, 2 H, 2 × ArH).
13C NMR (100 MHz): d = 7.3, 7.6 (CH3), 28.5, 29.1 (CH2), 51.7
(CH), 76.5 (COH), 120.1, 123.2, 127.5 (ArCH), 131.2, 140.1, 144.3
(ArC).
To a green suspension of Li metal (49 mg, 7 mmol) and DTBB (20
mg, 0.075 mmol) in THF (2 mL) cooled at –70 °C was added drop-
wise a soln of acenaphthylene (152 mg, 1 mmol) in THF (2 mL).
After the mixture was stirred for 2 h at the same temperature, the ex-
cess lithium was filtered off and washed with THF (2 mL). Then,
the corresponding electrophile (2.2 mmol) was added dropwise and
the mixture was stirred for 1 h and the temperature was allowed to
rise to –30 °C (1 h). The resulting mixture was hydrolysed with H2O
(5 mL) and the temperature was allowed to rise to r.t. The mixture
was extracted with EtOAc (3 × 10 mL), the organic layer was dried
(anhyd MgSO4) and the solvents were evaporated (15 Torr). The re-
sulting residue was then purified by column chromatography (silica
gel, hexane–EtOAc) or recrystallised (hexane–EtOAc) to afford the
corresponding product(s).
MS: m/z (%) = 326 (1) [M+], 279 (12), 222 (11), 194 (17), 193
(100), 155 (14), 154 (98), 153 (34), 152 (26), 87 (30), 57 (15).
When the reaction was performed under Barbier conditions, a mix-
ture of acenaphthylene (152 mg, 1 mmol) and the corresponding
electrophile (3 mmol) in THF (2 mL) was added dropwise to a green
suspension of Li metal (49 mg, 7 mmol) and DTBB (20 mg, 0.075
mmol) in THF (2 mL) cooled at –70 °C. The mixture was stirred for
2 h at the same temperature and then it was hydrolysed with H2O (5
mL) and the temperature was allowed to rise to r.t. After the workup
described above, the resulting residue was purified by column chro-
matography (silica gel, hexane–EtOAc) to afford the corresponding
product(s).
Anal. Calcd for C22H30O2·0.5H2O: C, 78.76; H, 9.31. Found: C,
78.45; H, 9.34.
3-(1,2-Dihydroacenaphthylen-1-yl)pentan-3-ol (7b)
Yellow oil; yield: 38%; tR = 16.6 min; Rf = 0.44 (hexane–EtOAc,
8:2).
IR (film): 3479 (OH), 3047 (=CH) cm–1.
1H NMR (400 MHz): d = 0.88 (t, J = 7.5 Hz, 3 H, CH3), 0.99 (t,
J = 7.5 Hz, 3 H, CH3), 1.39–1.50 (m, 3 H, CH2CH3, OH), 1.58–1.67
(m, 2 H, CH2CH3), 3.27–3.48 (m, 2 H, ArCH2), 3.95–3.99 (m, 1 H,
CH), 7.23–7.26 (m, 1 H, ArH), 7.40–7.47 (m, 3 H, 3 × ArH), 7.57–
7.64 (m, 2 H, 2 × ArH).
Global yields and ratios 6:7 are given in Table 1. Isolated yields and
physical, analytical and spectroscopic data, as well as literature ref-
erences for known compounds, follow.
13C NMR (100 MHz): d = 7.48, 7.78 (CH3), 28.3, 29.3, 33.5 (CH2),
50.6 (CH), 77.0 (COH), 118.9, 121.2, 122.3, 123.1, 127.6, 127.7
(ArCH), 131.4, 139.8, 144.4, 145.6 (ArC).
MS: m/z (%) = 240 (2) [M+], 156 (43), 155 (32), 154 (100), 153
(63), 152 (35), 87 (26).
trans-2,2¢-(1,2-Dihydroacenaphthylene-1,2-diyl)dipropan-2-ol
(6a)
Colourless solid; yield: 17%; mp 105 °C (hexane–EtOAc);
tR = 16.6 min; Rf = 0.11 (hexane–EtOAc, 8:2).
IR (KBr): 3381 (OH), 3050 (=CH) cm–1.
HRMS: m/z calcd for C17H20O: 240.1514; found: 240.1487.
1H NMR (400 MHz): d = 0.86 (s, 6 H, 2 × CH3), 1.41 (s, 6 H, 2 ×
CH3), 2.69 (s, 2 H, 2 × OH), 3.79 (s, 2 H, 2 × CH), 7.40 (d, J = 7.0
Hz, 2 H, 2 × ArH), 7.45–7.50 (m, 2 H, 2 × ArH), 7.67 (d, J = 8.0 Hz,
2 H, 2 × ArH).
13C NMR (100 MHz): d = 24.9, 28.9 (CH3), 57.7 (CH), 73.4 (COH),
120.6, 123.4, 127.5 (ArCH), 131.2, 139.7, 144.3 (ArC).
trans-3,3¢-(1,2-Dihydroacenaphthylene-1,2-diyl)bis(2,4-dimeth-
ylpentan-3-ol) (6c)
Colourless crystals; yield: 43%; mp 162 °C (hexane–EtOAc);
tR = 21.3 min; Rf = 0.23 (hexane–EtOAc, 9:1).
IR (KBr): 3403 (OH), 3054 (=CH) cm–1.
MS: m/z (%) = 270 (1) [M+], 179 (53), 155 (13), 154 (100), 153
(42), 152 (32), 57 (22).
1H NMR (400 MHz): d = 0.31 (d, J = 7.2 Hz, 6 H, 2 × CH3), 0.51
(d, J = 7.2 Hz, 6 H, 2 × CH3), 1.04 (d, J = 6.6 Hz, 6 H, 2 × CH3),
1.32 (d, J = 6.6 Hz, 6 H, 2 × CH3), 1.71 [sept, J = 6.6 Hz, 2 H, 2 ×
CH(CH3)2], 2.57 [sept, J = 7.2 Hz, 2 H, 2 × CH(CH3)2], 3.03 (br, 2
H, 2 × OH), 4.45 (s, 2 H, 2 × ArCH), 7.36 (d, J = 6.9 Hz, 2 H, 2 ×
Anal. Calcd for C18H22O2·0.67H2O: C, 76.56; H, 8.33. Found: C,
76.67; H, 8.10.
Synthesis 2008, No. 8, 1241–1248 © Thieme Stuttgart · New York

PAPER
Lithiation and Further Reaction of Acenaphthylene
1245
ArH), 7.41–7.45 (m, 2 H, 2 × ArH), 7.64 (d, J = 8.0 Hz, 2 H, 2 ×
ArH).
HRMS: m/z calcd for C19H18 [M+ – H2O]: 246.1409; found:
246.1486.
13C NMR (100 MHz): d = 18.1, 18.2, 18.7, 19.3 (CH3), 31.5, 34.0
[CH(CH3)2], 52.7 (CHCOH), 79.2 (COH), 120.9, 123.2, 127.3
(ArCH), 131.5, 140.7, 144.3 (ArC).
MS: m/z (%) = 346 (1) [M+ – 2 × H2O], 223 (15), 208 (18), 207
(100), 154 (40), 153 (27), 152 (32), 115 (18), 71 (44).
trans-1,1¢-(1,2-Dihydroacenaphthylene-1,2-diyl)dicyclopen-
tanol (6e)18
Yield: 5%; tR = 22.5 min.
MS: m/z (%) = 322 (2) [M+], 286 (12), 220 (48), 219 (33), 205 (14),
191 (27), 179 (11), 178 (19), 165 (14), 155 (13), 154 (100), 153
(33), 152 (27), 85 (20), 67 (12).
Anal. Calcd for C26H38O2: C, 81.62; H, 10.01. Found: C, 81.65; H,
10.40.
HRMS: m/z calcd for C22H24O [M+ – H2O]: 304.1827; found:
304.1778.
3-(1,2-Dihydroacenaphthylen-1-yl)-2,4-dimethylpentan-3-ol
(7c)
1-(1,2-Dihydroacenaphthylen-1-yl)cyclopentanol (7e)
White solid; yield: 59%; mp 57 °C (hexane–EtOAc); tR = 17.3 min;
Rf = 0.16 (hexane–EtOAc, 9:1).
IR (KBr): 3536, 3405 (OH), 3042 (=CH) cm–1.
1H NMR (300 MHz): d = 1.10–2.15 (m, 9 H, 4 × ring CH2, OH),
3.32–3.54 (m, 2 H, ArCH2), 3.84–3.88 (m, 1 H, CH), 7.23–7.28 (m,
1 H, ArH), 7.41–7.46 (m, 3 H, 3 × ArH), 7.57–7.66 (m, 2 H, 2 ×
ArH).
13C NMR (75 MHz): d = 23.8, 24.2, 34.4, 37.9, 39.6 (4 × ring CH2,
ArCH2CH), 53.3 (CH), 84.9 (COH), 119.1, 120.6, 122.2, 123.4,
127.5, 127.8 (ArCH), 131.5, 139.8, 144.7, 145.6 (ArC).
Yellow oil; yield: 35%; tR = 17.5 min; Rf = 0.34 (hexane–EtOAc,
9:1).
IR (film): 3585 (OH), 3047 (=CH) cm–1.
1H NMR (300 MHz): d = 0.64 (d, J = 7.0 Hz, 3 H, CH3), 0.83 (d,
J = 7.0 Hz, 3 H, CH3), 1.00 (d, J = 7.0 Hz, 6 H, 2 × CH3), 1.66 (s, 1
H, OH), 2.09–2.39 [m, 2 H, 2 × CH(CH3)2], 3.30–3.48 (m, 2 H,
CH2), 4.15–4.20 (m, 1 H, CH2CH), 7.24 (d, J = 7.0 Hz, 1 H, ArH),
7.38–7.45 (m, 2 H, 2 × ArH), 7.51–7.61 (m, 3 H, 3 × ArH).
13C NMR (100 MHz): d = 18.0, 18.1, 18.3, 18.8 (CH3), 32.2
[CH(CH3)2], 34.4 (CH2), 34.6 [CH(CH3)2], 48.8 (CH2CH), 79.7
(COH), 118.9, 121.6, 122.3, 122.7, 127.5, 127.6 (ArCH), 131.6,
139.3, 144.7, 147.7 (ArC).
MS: m/z (%) = 238 (6) [M+], 220 (13), 191 (11), 155 (13), 154
(100), 153 (48), 152 (32).
MS: m/z (%) = 268 (1) [M+], 207 (12), 155 (14), 154 (100), 153
(80), 152 (39), 115 (13), 71 (33).
Anal. Calcd for C17H18O: C, 85.67; H, 7.61. Found: C, 85.46; H,
7.48.
HRMS: m/z calcd for C19H24O: 268.1827; found: 268.1857.
trans-1,1¢-(1,2-Dihydroacenaphthylene-1,2-diyl)dicyclohexanol
(6f)
Colourless crystals; yield: 29%; mp 158 °C (hexane–EtOAc);
tR = 26.7 min; Rf = 0.24 (hexane–EtOAc, 8:2).
trans-(1,2-Dihydroacenaphthylene-1,2-diyl)bis(dicyclopropyl-
methanol) (6d)
Colourless crystals; yield: 68%; mp 151 °C (hexane–EtOAc);
tR = 24.7 min; Rf = 0.48 (hexane–EtOAc, 8:2).
IR (KBr): 3382 (OH), 3084, 3070 (=CH) cm–1.
1H NMR (300 MHz): d = –0.15–0.17, 0.31–0.62, 1.15–1.59 (3 × m,
20 H, 8 × ring CH2, 4 × ring CH), 2.29 (s, 2 H, 2 × OH), 4.28 (s, 2
H, 2 × ArCH), 7.42–7.53 (m, 4 H, 4 × ArH), 7.66 (d, J = 7.9 Hz, 2
H, 2 × ArH).
13C NMR (100 MHz): d = –1.1, –0.4, –0.0, 2.4 (ring CH2), 15.8,
17.8 (ring CH), 57.5 (ArCHCOH), 72.5 (COH), 120.7, 123.0, 127.2
(ArCH), 131.2, 140.5, 144.7 (ArC).
IR (KBr): 3390 (OH), 3045 (=CH) cm–1.
1H NMR (300 MHz): d = 0.86–2.17 (m, 22 H, 10 × ring CH2, 2 ×
OH), 3.73 (s, 2 H, 2 × CH), 7.26–7.50 (m, 4 H, 4 × ArH), 7.66 (d,
J = 8.1 Hz, 2 H, 2 × ArH).
13C NMR (75 MHz): d = 21.4, 21.7, 25.6, 32.9, 34.8 (ring CH2),
57.5 (CH), 74.1 (COH), 120.9, 123.3, 127.4 (ArCH), 131.1, 140.1,
144.3 (ArC).
MS: m/z (%) = 350 (1) [M+], 234 (19), 191 (13), 178 (14), 155 (14),
154 (100), 153 (26), 152 (18), 99 (26), 79 (17).
HRMS: m/z calcd for C24H26 [M+ – 2 × H2O]: 314.2035; found:
314.2059.
MS: m/z (%) = 356 (1) [M+ – H2O], 246 (24), 231 (14), 218 (16),
217 (18), 205 (39), 203 (17), 165 (10), 154 (46), 153 (14), 152 (23),
111 (100), 69 (54).
Anal. Calcd for C26H30O2: C, 83.38; H, 8.07. Found: C, 83.97; H,
8.34.
1-(1,2-Dihydroacenaphthylen-1-yl)cyclohexanol (7f)
Yellow oil; yield: 31%; tR = 18.3 min; Rf = 0.47 (hexane–EtOAc,
8:2).
IR (film): 3444 (OH), 3046 (=CH) cm–1.
1H NMR (300 MHz): d = 1.05–2.04 (m, 11 H, 5 × ring CH2, OH),
3.32–3.49 (m, 2 H, ArCH2), 3.71–3.76 (m, 1 H, ArCH), 7.26 (d,
J = 6.6 Hz, 1 H, ArH), 7.40–7.50 (m, 3 H, 3 × ArH), 7.57–7.65 (m,
2 H, 2 × ArH).
13C NMR (100 MHz): d = 21.5, 21.6, 25.7, 33.1, 33.7, 35.4 (5 × ring
CH2, ArCH2CH), 54.7 (CH), 74.3 (COH), 118.9, 121.5, 122.3,
123.2, 127.5, 127.7 (ArCH), 131.4, 139.7, 144.5, 145.2 (ArC).
Dicyclopropyl(1,2-dihydroacenaphthylen-1-yl)methanol (7d)
Yellow oil; yield: 10%; tR = 18.2 min; Rf = 0.50 (hexane–EtOAc,
8:2).
IR (film): 3584, 3485 (OH), 3082 (=CH) cm–1.
1H NMR (300 MHz): d = 0.02–0.61, 0.76–0.95 (2 × m, 10 H, 4 ×
ring CH2, 2 × ring CH), 1.22 (s, 1 H, OH), 3.43–3.62 (m, 2 H,
ArCH2), 3.98–4.04 (m, 1 H, ArCH), 7.27 (d, J = 6.7 Hz, 1 H, ArH),
7.41–7.48 (m, 2 H, 2 × ArH), 7.57–7.65 (m, 3 H, 3 × ArH).
13C NMR (75 MHz): d = –1.5, –1.1, 1.0, 2.5 (ring CH2), 16.2, 16.6
(ring CH), 33.7 (CH2), 55.1 (CH), 73.4 (COH), 118.7, 121.6, 122.2,
122.9, 127.5 (ArCH), 131.4, 139.9, 144.8, 146.0 (ArC).
MS: m/z (%) = 252 (3) [M+], 155 (14), 154 (100), 153 (37), 152
(24), 99 (12), 81 (13).
MS: m/z (%) = 264 (1) [M+], 155 (13), 154 (100), 153 (49), 152
HRMS: m/z calcd for C18H20O: 252.1514; found: 252.1490.
(43), 151 (12), 111 (73), 69 (51).
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V. J. Lillo et al.
PAPER
trans-2,2¢-(1,2-Dihydroacenaphthylene-1,2-diyl)diadamantan-
2-ol (6g)
Colourless crystals; yield: 77%; mp 116 °C (dec) (hexane–EtOAc);
Rf = 0.54 (hexane–EtOAc, 8:2).
IR (KBr): 3545, 3437 (OH), 3047 (=CH) cm–1.
1H NMR (300 MHz): d = 1.08 [s, 9 H, C(CH3)3], 1.10 [s, 9 H,
C(CH3)3], 1.54 (br, 2 H, 2 × OH), 3.53, 3.73, 3.87, 4.36 (4 × s, 4 H,
2 × CHCHOH, 2 × CHCHOH), 7.25–7.27 (m, 1 H, ArH), 7.42–7.51
(m, 3 H, 3 × ArH), 7.61–7.66 (m, 2 H, 2 × ArH).
IR (KBr): 3584, 3550, 3445 (OH), 3047 (=CH) cm–1.
1H NMR (300 MHz): d = 0.29 (s, 2 H, 2 × OH), 1.41–2.38 (m, 28
H, 10 × ring CH2, 8 × ring CH), 4.35 (s, 2 H, ArCH), 7.27 (d, J = 7.3
Hz, 2 H, 2 × ArH), 7.41–7.47 (m, 2 H, 2 × ArH), 7.63 (d, J = 8.1 Hz,
2 H, 2 × ArH).
13C NMR (75 MHz): d = 27.0, 27.4, 33.8, 36.0 (ring CH), 33.2,
34.0, 34.5, 38.2 (ring CH2), 51.4 (ArCHCOH), 76.9 (COH), 121.7,
123.1, 127.2 (ArCH), 130.9, 140.2, 144.4 (ArC).
13C NMR (75 MHz): d = 27.3, 27.8 (CH3), 36.1, 36.5 [C(CH3)3],
47.4, 54.3 (CHCHOH), 84.0, 86.1 (CHCHOH), 118.7, 123.0, 123.3,
123.5, 127.3, 128.2 (ArCH), 131.0, 140.6, 142.6, 148.7 (ArC).
MS: m/z (%) = 326 (1) [M+], 165 (30), 155 (13), 154 (100), 153
(44), 152 (23).
Anal. Calcd for C22H30O2·0.33H2O: C, 79.47; H, 9.30. Found: C,
79.50; H, 9.62.
MS: m/z (%) = 454 (1) [M+], 286 (17), 155 (13), 154 (100), 153
(18), 152 (21), 151 (75).
Diastereomer 6i¢¢¢
Colourless solid; yield: 10%; mp 42 °C (hexane–EtOAc); tR = 20.1
min; Rf = 0.50 (hexane–EtOAc, 8:2).
IR (KBr): 3378 (OH), 3049 (=CH) cm–1.
HRMS: m/z calcd for C32H34 [M+ – 2 × H2O]: 418.2661; found:
418.2674.
trans-(1,2-Dihydroacenaphthylene-1,2-diyl)bis(diphenylmeth-
anol) (6h)
Colourless crystals; yield: 72%; mp 249 °C (hexane–EtOAc);
Rf = 0.28 (hexane–EtOAc, 8:2).
1H NMR (300 MHz): d = 1.04 [s, 18 H, 2 × C(CH3)3], 1.58 (br, 2 H,
2 × OH), 3.76–3.78, 3.92–3.94 (2 × m, 4 H, 2 × CHCHOH, 2 ×
CHCHOH), 7.25 (d, J = 6.1 Hz, 2 H, 2 × ArH), 7.40–7.46 (m, 2 H,
2 × ArH), 7.59 (d, J = 8.1 Hz, 2 H, 2 × ArH).
13C NMR (75 MHz): d = 26.6 (CH3), 36.6 [C(CH3)3], 52.1
(CHCHOH), 80.8 (CHCHOH), 118.8, 122.8, 127.5 (ArCH), 131.2,
137.1, 147.9 (ArC).
MS: m/z (%) = 326 (1) [M+], 279 (16), 167 (37), 154 (10), 150 (11),
149 (100), 71 (11), 57 (15).
HRMS: m/z calcd for C18H19O [M+ – H2O, – C(CH3)3]: 251.1441;
found: 251.1392.
IR (KBr): 3526, 3372 (OH), 3052 (=CH) cm–1.
1H NMR (300 MHz): d = 3.38 (br, 2 H, 2 × OH), 4.67 (s, 2 H, 2 ×
CH), 6.06 (d, J = 7.0 Hz, 2 H, 2 × ArH), 7.04–7.10 (m, 11 H, 11 ×
ArH), 7.29–7.38 (m, 11 H, 11 × ArH), 7.51 (d, J = 8.1 Hz, 2 H, 2 ×
ArH).
13C NMR (75 MHz): d = 57.7 (CH), 81.2 (COH), 121.2, 123.5,
126.9, 127.2, 127.3, 127.4, 127.5, 127.8, 128.3 (ArCH), 130.8,
141.2, 142.7, 142.9, 145.2 (ArC).
MS: m/z (%) = 500 (1) [M+ – H2O], 318 (25), 317 (12), 316 (10),
315 (11), 241 (12), 183 (22), 182 (74), 181 (11), 153 (13), 152 (86),
151 (18), 150 (12), 105 (100), 77 (45), 76 (10), 51 (11).
1-(1,2-Dihydroacenaphthylen-1-yl)-2,2-dimethylpropan-1-ol
(7i)
Yellow solid; yield: 14%; mp 56 °C (hexane–EtOAc); tR = 16.5
min; Rf = 0.59 (hexane–EtOAc, 8:2).
IR (film): 3581, 3479 (OH), 3036 (=CH) cm–1.
Anal. Calcd for C38H30O2: C, 88.00; H, 5.83. Found: C, 88.67; H,
6.05.
1H NMR (300 MHz): d = 1.12 [s, 9 H, C(CH3)3], 1.56 (br, 1 H, OH),
3.27–3.34, 3.62–3.68, 3.95–4.01 (3 × m, 4 H, CH2, CH2CH,
CHOH), 7.25–7.30 (m, 2 H, 2 × ArH), 7.42–7.58 (m, 2 H, 2 × ArH),
7.61–7.65 (m, 2 H, 2 × ArH).
13C NMR (100 MHz): d = 27.1 (CH3), 31.6 (CH2), 35.6 [C(CH3)3],
45.3 (CH2CH), 81.9 (CHOH), 118.3, 119.2, 122.1, 123.1, 127.8,
128.1 (ArCH), 131.3, 139.1, 145.6, 148.5 (ArC).
trans-1,1¢-(1,2-Dihydroacenaphthylene-1,2-diyl)bis(2,2-dimeth-
ylpropan-1-ol) (6i)
Diastereomer 6i¢
Yellow solid; yield: 38%; mp 51 °C (hexane–EtOAc); tR = 19.1
min; Rf = 0.31 (hexane–EtOAc, 8:2).
IR (KBr): 3444 (OH), 3048 (=CH) cm–1.
1H NMR (300 MHz): d = 0.88 [s, 18 H, 2 × C(CH3)3], 1.47 (br, 2 H,
2 × OH), 3.70–3.71 (m, 2 H, 2 × CHCHOH), 4.08–4.15 (m, 2 H, 2
× CHCHOH), 7.38 (d, J = 6.9 Hz, 2 H, 2 × ArH), 7.43–7.49 (m, 2
H, 2 × ArH), 7.63 (d, J = 8.1 Hz, 2 H, 2 × ArH).
MS: m/z (%) = 240 (9) [M+], 155 (13), 154 (100), 153 (54), 152
(25).
HRMS: m/z calcd for C17H20O: 240.1514; found: 240.1492.
13C NMR (75 MHz): d = 27.4 (CH3), 36.5 (CHCHOH), 49.9
[C(CH3)3], 83.7 (CHCHOH), 120.2, 123.0, 128.0 (ArCH), 131.1,
139.5, 147.3 (ArC).
MS: m/z (%) = 326 (3) [M+], 165 (19), 155 (14), 154 (100), 153
(39), 152 (19).
Acknowledgment
This work was generously supported by the Dirección General de
Enseñanza Superior (DGES) of the current Spanish Ministerio de
Educación y Ciencia [MEC; Consolider Ingenio 2010 (CSD2007-
00006)] and the Generalitat Valenciana (GRUPOS05/052). V.J.L.
thanks the University of Alicante for a predoctoral fellowship. We
also thank MEDALCHEMY S.L. for a gift of chemicals.
HRMS: m/z calcd for C22H30O2: 326.2246; found: 326.2221.
Diastereomer 6i¢¢
White solid; yield: 21%; mp 72 °C (hexane–EtOAc); tR = 19.4 min;
Rf = 0.47 (hexane–EtOAc, 8:2).
Synthesis 2008, No. 8, 1241–1248 © Thieme Stuttgart · New York

PAPER
Lithiation and Further Reaction of Acenaphthylene
1247
(11) For an NMR and theoretical study on the aromaticity of the
acenaphthylene dianion and related systems, see: Minsky,
A.; Meyer, A. V.; Hafner, K.; Rabinovitz, M. J. Am. Chem.
Soc. 1983, 105, 3975.
(12) The lithiation of acenaphthylene in tetrahydrofuran, with or
without liquid ammonia, followed by trapping of the anionic
intermediates with an alkyl halide leads mainly to substitu-
tion at position 1 or 5, respectively (see reference 7h).
(13) For a review, see: Alonso, F.; Yus, M. Recent Res. Dev. Org.
Chem. 1997, 1, 397.
(14) In reference 10b, the lithiation of acenaphthene (4) with an
excess of n-butyllithium, followed by treatment with
benzophenone, gave 32% of a diol resulting from 1,5-
disubstitution. The physical and spectroscopic data of this
diol coincide with those of our compound 6h in which the
electrophilic fragments occupy the 1,2-positions.
References
(1) For reviews on arene-catalysed lithiation, see: (a) Yus, M.
Chem. Soc. Rev. 1996, 25, 155. (b) Ramón, D. J.; Yus, M.
Eur. J. Org. Chem. 2000, 225. (c) Yus, M. Synlett 2001,
1197. (d) Yus, M. In The Chemistry of Organolithium
Compounds, Part 1, Vol. 1; Rappoport, Z.; Marek, I., Eds.;
Wiley & Sons: Chichester, 2004, Chap. 11. For a polymer-
supported arene-catalysed version of this reaction, see:
(e) Gómez, C.; Ruiz, S.; Yus, M. Tetrahedron Lett. 1998, 39,
1397. (f) Gómez, C.; Ruiz, S.; Yus, M. Tetrahedron 1999,
55, 7017. (g) Yus, M.; Candela, P.; Gómez, C. Tetrahedron
2002, 58, 6207. (h) Alonso, F.; Candela, P.; Gómez, C.;
Yus, M. Adv. Synth. Catal. 2003, 345, 275. (i) Candela, P.;
Gómez, C.; Yus, M. Russ. J. Org. Chem. 2004, 40, 795.
(2) For a review, see: Guijarro, D.; Yus, M. Recent Res. Dev.
Org. Chem. 1998, 2, 713.
(15) (a) Crystal data, excluding structure factors, have been
deposited at the Cambridge Crystallographic Data Centre as
supplementary publication numbers as follows [copies of the
data can be obtained, free of charge, on application to
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; Fax:
+44 (1223)336033; E-mail: deposit@ccdc.cam.ac.uk]: 6c,
CCDC 667608: C26H38O2, M = 382.56, tetragonal, space
group I41/a, Z = 8, a = 10.2698(9) Å, b = 10.2698(9) Å,
c = 42.579(7) Å, V = 4490.7(10) Å3, Dc = 1.132 Mg·m–3,
l = 0.71073 Å, m = 0.069 mm–1, F(000) = 1680, T = 25 1
°C; 6d, CCDC 667607: C26H30O2, M = 374.50, monoclinic,
space group P21/c, a = 12.179(3) Å, b = 7.5565(17) Å,
c = 22.867(5) Å, b = 100.135(5)°, V = 2071.6(8) Å3, Z = 4,
Dc = 1.201 Mg·m–3, l = 0.71073 Å, m = 0.074 mm–1,
F(000) = 808, T = 23 1 °C; 6f, CCDC 667606: C24H30O2,
M = 350.22, impure with C12H22O2, triclinic, space group
P1, a = 10.7269(12) Å, b = 10.9803(12) Å, c = 11.9786(13)
Å, a = 69.905(2)°, b = 68.552(2)°, g = 77.201(2)°, V =
1225.8(2) Å3, Z = 2, Dc = 1.218 Mg·m–3, l = 0.71073 Å,
m = 0.076 mm–1, F(000) = 490, T = 25 1 °C; 6h, CCDC
667609: C38H30O2, M = 518.62, triclinic, space group P1,
a = 11.448(3) Å, b = 13.297(4) Å, c = 18.863(5) Å,
a = 105.589(5)°, b = 90.034(7)°, g = 91.261(6)°, V =
2765.0(13) Å3, Z = 4, Dc = 1.246 Mg·m–3, l = 0.71073 Å,
m = 0.075 mm–1, F(000) = 1096, T = 25 1 °C. Data
collection was performed on a Bruker CCD-Apex
(3) For reviews, see: (a) Yus, M.; Foubelo, F. Rev. Heteroat.
Chem. 1997, 17, 73. (b) Yus, M.; Foubelo, F. In Targets in
Heterocyclic Systems; Attanasi, O. A.; Spinelli, D., Eds.;
Italian Society of Chemistry: Rome, 2002, 136–171.
(c) Yus, M. Pure Appl. Chem. 2003, 75, 1453. (d) Yus, M.;
Foubelo, F. Adv. Heterocycl. Chem. 2006, 91, 135.
(4) For reviews, see: (a) Nájera, C.; Yus, M. Trends Org. Chem.
1991, 2, 155. (b) Nájera, C.; Yus, M. Org. Prep. Proced. Int.
1995, 27, 383. (c) Nájera, C.; Yus, M. Recent Res. Dev. Org.
Chem. 1997, 1, 67. (d) Nájera, C.; Yus, M. Curr. Org.
Chem. 2003, 7, 867. (e) Nájera, C.; Sansano, J. M.; Yus, M.
Tetrahedron 2003, 59, 9255. (f) Chinchilla, R.; Nájera, C.;
Yus, M. Chem. Rev. 2004, 104, 2667. (g) Chinchilla, R.;
Nájera, C.; Yus, M. Tetrahedron 2005, 61, 3139. (h) See
also the Tetrahedron Symposium-in-Print issue devoted to
‘Functionalised Organolithium Compounds’ (Nájera, C.;
Yus, M., Eds.): Tetrahedron 2005, 61, 3125–3450. (i) Yus,
M.; Foubelo, F. In Functionalized Organometallics, Vol. 1;
Knochel, P., Ed.; Wiley-VCH: Weinheim, 2005, Chap. 2.
(j) Nájera, C.; Yus, M. In The Chemistry of Organolithium
Compounds, Vol. 2; Rappoport, Z.; Marek, I., Eds.; Wiley &
Sons: Chichester, 2006, Chap. 3. (k) Chinchilla, R.; Nájera,
C.; Yus, M. ARKIVOC 2007, (x), 152.
(5) For reviews, see: (a) Foubelo, F.; Yus, M. Trends Org.
Chem. 1998, 7, 1. (b) Foubelo, F.; Yus, M. Curr. Org.
Chem. 2005, 9, 459.
diffractometer, based on three w-scan runs (starting = –34°)
at values f = 0°, 120° and 240° with the detector at 2q =
–32°. For each of these runs, 606 frames were collected at
0.3° intervals and 20 s per frame. An additional run at f = 0°
of 100 frames was collected to improve redundancy. The
diffraction frames were integrated using the program
SAINT15b and the integrated intensities were corrected for
Lorentz polarisation effects with SADABS.15c The structure
was solved by direct methods15d and refined to all 2463
unique Fo2 by the full-matrix least-squares technique.15d All
the hydrogen atoms were placed at idealised positions and
refined as rigid atoms. Final wR2 = 0.1300 for all data and
246 parameters; R1 = 0.0424 for 2051 Fo > 4s(Fo).
(b) SAINT Version 6.02A: Area-Detector Integration
Software; Siemens Industrial Automation, Inc.: Madison
WI, 1995. (c) Sheldrick, G. M. SADABS: Area-Detector
Absorption Correction; University of Göttingen: Göttingen
Germany, 1996. (d) Sheldrick, G. M. SHELX-97 (Includes
SHELXS-97, SHELXL-97 and CIFTAB) Program for
Crystal Structure Analysis (Release 97-2); University of
Göttingen: Göttingen Germany, 1998.
(6) For reviews, see: (a) Guijarro, A.; Gómez, C.; Yus, M.
Trends Org. Chem. 2000, 8, 65. (b) Alonso, F.; Radivoy,
G.; Yus, M. Russ. Chem. Bull. 2003, 52, 2563. (c) Alonso,
F.; Yus, M. Chem. Soc. Rev. 2004, 33, 284.
(7) For mechanistic and reactivity studies on arene dianions,
see: (a) Yus, M.; Herrera, R. P.; Guijarro, A. Tetrahedron
Lett. 2001, 42, 3455. (b) Yus, M.; Herrera, R. P.; Guijarro,
A. Chem. Eur. J. 2002, 8, 2574. (c) Yus, M.; Herrera, R. P.;
Guijarro, A. Tetrahedron Lett. 2003, 44, 1309. (d) Herrera,
R. P.; Guijarro, A.; Yus, M. Tetrahedron Lett. 2003, 44,
1313. (e) Yus, M.; Herrera, R. P.; Guijarro, A. Tetrahedron
Lett. 2006, 47, 6267. (f) Melero, C.; Pérez, H.; Guijarro, A.;
Yus, M. Tetrahedron Lett. 2007, 48, 4105. (g) Melero, C.;
Guijarro, A.; Baumann, V.; Pérez-Jiménez, A. J.; Yus, M.
Eur. J. Org. Chem. 2007, 5514. (h) Melero, C.; Herrera, R.
P.; Guijarro, A.; Yus, M. Chem. Eur. J. 2007, 13, 10096.
(8) (a) Ristagno, C. V.; Lawler, R. G. Tetrahedron Lett. 1973,
159. (b) Van Loo, M. E.; Lugtenburg, J.; Cornelisse, J. Eur.
J. Org. Chem. 1998, 1907.
(9) (a) Laguerre, M.; Félix, G.; Dunogués, J.; Calas, R. J. Org.
Chem. 1979, 44, 4275. (b) Fedushkin, I. L.; Petroskaya, T.
V.; Bochkarev, M. N.; Dechert, S.; Schuman, H. Angew.
Chem. Int. Ed. 2001, 40, 2474.
(10) (a) Eisch, J. J.; Fichter, K. C. J. Org. Chem. 1984, 49, 4631.
(b) Cantrell, T. S. Tetrahedron Lett. 1973, 1803.
(16) For a recent account, see: Clayden, J.; Yasin, S. A. New J.
Chem. 2002, 26, 191.
(17) To the best of our knowledge, there is only one case reported
in the literature in which the lithiation of acenaphthylene(1)
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V. J. Lillo et al.
PAPER
in the presence or absence of liquid ammonia, followed by
treatment with iodomethane, gave 1,2-disubstitution, in 33%
yield; see: Usami, S.; Hasegawa, K.; Kato, T.; Nakamura, S.;
Tsukashima, H. Nenryo Kyokaishi 1986, 65, 996; Chem.
Abstr. 1987, 106, 159278.
(18) As this compound was isolated in a very low yield, and the
isolated product was ca. 70% pure (by GLC), the 1H and 13
NMR assignments were difficult to undertake.
C
Synthesis 2008, No. 8, 1241–1248 © Thieme Stuttgart · New York