Iron-Catalyzed C-Allylating Partial Dearomatization of Naphthols

Article abstract of DOI:10.1055/s-0035-1560909

The iron complex Bu₄N[Fe(CO)₃(NO)] (TBA[Fe]) catalyzes the intermolecular allylation of naphthol derivatives to give the corresponding partially dearomatized allylated chromenones in good to excellent yields. The scope and limitations are reported. An efficient decarboxylative intramolecular C-allylation, starting from allyl naphthyl carbonates, was developed. From a mechanistic point of view, the overall process is the result of a fast O-allylation followed by a sigmatropic rearrangement to the desired product.

Full text of DOI:10.1055/s-0035-1560909

SYNTHESIS
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© Georg Thieme Verlag Stuttgart · New York
2016, 48, 340–350
feature
340
B. Heid, B. Plietker
Feature
Synthesis
Iron-Catalyzed C-Allylating Partial Dearomatization of Naphthols
Berenice Heid
Bernd Plietker*
i-BuO
O
+
OH
Institut für Organische Chemie, Universität Stuttgart,
Pfaffenwaldring 55, 70569 Stuttgart, Germany
bernd.plietker@oc.uni-stuttgart.de
O
TBA[Fe] (cat.)
NHC ligand (cat.)
O
MeCN, 100 °C
O
or:
O
O
Received: 18.09.2015
Accepted after revision: 16.10.2015
Published online: 24.11.2015
Biosynthesis of PPAPs
DOI: 10.1055/s-0035-1560909; Art ID: ss-2015-t0546-fa
OH
O
OH
O
O-allylation/
rearrangement
R
R
Abstract The iron complex Bu4N[Fe(CO)3(NO)] (TBA[Fe]) catalyzes the
intermolecular allylation of naphthol derivatives to give the corre-
sponding partially dearomatized allylated chromenones in good to ex-
cellent yields. The scope and limitations are reported. An efficient de-
carboxylative intramolecular C-allylation, starting from allyl naphthyl
carbonates, was developed. From a mechanistic point of view, the over-
all process is the result of a fast O-allylation followed by a sigmatropic
rearrangement to the desired product.
HO
OH
HO
OH
Ar
O
(1)
HO
O
O
prenylation/
cyclization
Key words iron catalysis, allylation, decarboxylation, dearomatiza-
tion, substitution, rearrangement
Tunge (2009): Fe-catalyzed decarboxylative O-allylation
TBA[Fe] (cat.)
The synthesis of carbocyclic products with defined ste-
reochemistry remains a central topic within organic syn-
thesis. Amongst the various strategies developed to date,
dearomatization of aromatic compounds has only recently
attracted significant attention. This is mostly due to the sig-
nificant amount of energy required to overcome the reso-
nance energy present in aromatic groups.1
R
O
PPh
3 (cat.)
O
(2)
O
O
R
DMF, 80 °C
O
R
Plietker (2013): Regioselective Fe-catalyzed O-allylation
In nature, dearomatization is usually the consequence
of an allyl phenyl ether rearrangement, that is a [3,3]-sig-
matropic Claisen rearrangement. Within the past years, our
group has been involved in developing short total syntheses
of polyprenylated polycyclic acylphloroglucines (PPAP).2
Biosynthesis studies of these natural products revealed that
per-prenylation of an acylphloroglucine derivative via se-
quences of O-allylation and subsequent allyl phenyl ether
rearrangement results in the formation of a tris-prenylated
cyclohexadienones, which undergo further prenylation and
cyclization to give natural products with the unusual
[3.3.1]-nonatrione core (Scheme 1, eq. 1).3 Parallel to our
synthetic investigations, we developed efficient protocols
for regioselective Tsuji–Trost-type allylations by using the
iron complex Bu4N[Fe(CO)3(NO)] (TBA[Fe]).4 On the basis of
OH
TBA[Fe] (cat.)
TRIANIS (cat.)
O
R
R
(3)
(4)
i-BuO
O
O
THF, 80 °C
You (2013): Enantioselective Pd-catalyzed C-allylation
Pd2(dba)3 (cat.)
Trost ligand (cat.)
OH
O
TBA[Fe] (cat.)
NHC ligand (cat.)
(5)
i-BuO
O
MeCN, 100 °C
this work
O
Scheme 1 O- versus C-allylation: state of research
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, 340–350

341
B. Heid, B. Plietker
Feature
Synthesis
this work, the group of Tunge reported a TBA[Fe]-catalyzed
decarboxylative O-allylation by using aryl allyl carbonates
as starting materials (Scheme 1, eq. 2).5
N
N
N
N
Whereas only moderate regioselectivities were reported
for the decarboxylative intramolecular O-allylation, our
group was later on able to show that the use of triazolium-
based carbene ligands allows a selective ipso-substitution
to take place in the intermolecular O-allylation of various
phenol derivatives (Scheme 1, eq. 3).6
PF6
L1
Cl
N
N
L3
PF6
L2
At the same time, landmark reports on a dearomatizing
palladium-catalyzed Tsuji–Trost allylation of dialkylnaph-
thols were reported by You (Scheme 1, eq. 4).7 On the basis
of their experimental results, they proposed that direct C-
allylation takes place instead of O-allylation–[3,3]-sigma-
tropic rearrangement. In light of the potential application
in total synthesis and with regard to our and others’ previ-
ous work in allylating dearomatization, we became inter-
ested in developing a TBA[Fe]-catalyzed version of You’s
transformation. Herein we report the successful realization
of this concept (Scheme 1, eq. 5).
We initiated our studies by employing 1,3-dimethyl-2-
naphthol (1) as starting material, and were pleased to find
that the reaction in tetrahydrofuran as a solvent and by us-
ing TBA[Fe] (10 mol%) and NHC-ligand L1 (12 mol%) (Figure
1) already gave the desired product 3 in a promising yield of
62% (Table 1, entry 1).
N
N
N
N
Ph
Ph
P
PF6
L4
PF6
L5
L6
Figure 1 Ligand structures
The carbonate structure has a strong influence on the reac-
tivity. Moderate reactivities were observed alongside with
significant formation of the O-allylation product B. These
results indicate the process to be rather a sequence of O-al-
lylation–sigmatropic rearrangement than a direct dearoma-
tizing C-allylation. To prove this assumption, the O-allylated
product 15 (see product B, entry 2), was reacted at 80 °C for
18 hours in acetonitrile; this resulted in a 1:1 mixture of 15
and 14. This result proves that an iron-catalyzed O-allyla-
tion followed by [3,3]-sigmatropic rearrangement takes
place. Introduction of additional substituents at the olefinic
moiety led to a significant erosion in reactivity (entries 6
A subsequent evaluation of the scope and limitations
was performed. Various substituted allylic carbonates were
employed under the standard reaction conditions (Table 2).
Biographical sketches
Berenice Heid was born in
1987. She obtained her diploma
degree in Chemistry at the Uni-
versity of Stuttgart (Germany)
in 2012. Since graduation she
has been a Ph.D. student in the
group of Prof. Dr. B. Plietker at
the same university. She is fo-
cusing on the development of
iron-catalyzed allylic substitu-
tions and dearomatizations.
Bernd Plietker studied chem-
istry in Münster, Germany, and
received his diploma degree in
1995. He obtained his Dr. rer.
nat. under the supervision of
Peter Metz in the field of intra-
molecular Diels–Alder reactions
at the Technische Universität
Dresden, Germany. He spent
one year as a postdoc with Jan-
Erling Bäckvall, Stockholm Uni-
versitet, Sweden, followed by a
second year with Barry M. Trost,
Stanford University, USA, work-
ing in the field of palladium ca-
talysis. In 2001 he founded a
research group at the Universi-
tät Dortmund, Germany, sup-
ported by a Liebig fellowship of
the Fonds der chemischen In-
dustrie and an Emmy-Noether-
grant of the Deutsche For-
schungsgemeinschaft.
Since
2007 he has been a professor of
organic chemistry at the Univer-
sität Stuttgart, Germany. The
research in his group focuses on
the development of sustainable
catalytic transformations by
employing highly oxidized ru-
thenium complexes or subva-
lent iron complexes in catalysis
and natural product synthesis.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, 340–350

342
B. Heid, B. Plietker
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Table 1 Optimization of the Reaction Conditions: Variation of Solvent
Table 2 Iron-Catalyzed Partially Dearomatizing C-Allylation: Allyl Car-
bonate Scope
and Liganda
TBA[Fe] (10 mol%)
L (12 mol%)
KOt-Am (14 mol%)
En- Carbonate
try
Product Aa
Product Ba
O
O
Oi-Bu
+
O
OH
solvent
co-solvent
18 h
O
1
2
3
O
60 °C
O
Oi-Bu
1b
Ph
Ph
4
Entry
Solvent
Co-solventb
Ligandc
Yield of 3 (%)d
13 (54)
14 (12)
16 (14)
17 (43)
18 (4)
1
2
THF
–
–
–
–
–
–
–
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L2
L3
L4
L5
L6
62
18
49
56
49
80 (73)e
30
81
72
75
91
–
O
CH2Cl2
toluene
MTBE
DMF
O
O
Oi-Bu
O
3
2b
4
5
6
5
15 (63)
6
MeCN
7
1,4-dioxane
MeCN
O
O
8
THF
3b
4c
5c
O
Oi-Bu
9
MeCN
CH2Cl2
MTBE
THF
10
11
12
13
14
15
MeCN
MeCN
MeCN
THF
O
MeCN
THF
90
84
–
O
O
Oi-Bu
MeCN
THF
MeCN
THF
5
a Reaction conditions: Bu4N[Fe(CO)3NO] (10 mol%), ligand (12 mol%), potas-
sium tert-pentoxide (KOt-Am) (14 mol%), naphthol 1 (0.2 mmol), carbonate
2 (0.2 mmol), THF (0.05 mmol), MeCN (1 mL), 60 °C.
b Co-solvent (0.05 mmol).
O
O
c For ligand structures, see Figure 1.
O
Oi-Bu
Ph
d Yield of the crude reaction mixture determined by 1H NMR analysis; mesity-
lene (0.2 mmol) used as internal standard.
Ph
e Isolated yield.
7
and 8). Using monosubstituted olefins possessing different
substituents at the quaternary allylic C-atom led to the for-
mation of the desired product in low to good yields along
with varying amounts of the undesired O-allylation prod-
uct.
A screening of the naphthol scope using carbonate 2 as
allylating agent resulted in significantly improved yields
and conversions (Table 3). Various substituted naphthol de-
rivatives were successful dearomatized. Importantly, func-
tional groups such as halides and carbonyl groups remain
intact. Hence, this transformation sets the stage for employ-
ing di- and monosubstituted β-naphthols as building blocks
to allow the generation of molecular complexity within a
few synthetic operations. Unfortunately, the use of 1-naph-
thols was not successful so far.
O
O
O
6c
O
Oi-Bu
8
9
19 (26)
20 (4)
O
O
O
7c
O
Oi-Bu
22 (43)
21 (10)
O
O
8c
O
O
Oi-Bu
10
24 (39)
23 (23)
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, 340–350

343
B. Heid, B. Plietker
Feature
Synthesis
En- Carbonate
try
Product Aa
Product Ba
Entry Product
Yield (%)a
I
O
O
6c
32
33
34
66
65
80
O
9c
O
O
Oi-Bu
Ph
Ph
11
25 (11)
Ph
O
7c
O
10c
O
O
Oi-Bu
Bu
Bu
12
Bu
26 (18)
27 (32)
O
a Isolated yield (%) given in parentheses.
8d
b Reaction conditions: TBA[Fe] (1 mol%), L2 (3 mol%), KOt-Am (5 mol%), naph-
thol (0.2 mmol), carbonate (0.2 mmol), EtOAc as co-solvent (0.05 mmol),
MeCN (1 mL), 60 °C.
c Reaction conditions: TBA[Fe] (5 mol%), L2 (7 mol%), KOt-Am (9 mol%), naph-
thol (0.2 mmol), carbonate (0.2 mmol), THF as co-solvent (0.05 mmol), MeCN
(0.5 mL), 60 °C.
Br
O
9d
35
36
72
19
Table 3 Scope and Limitations of Naphthol Derivatives
Entry Product
Yield (%)a
O
t-BuO
10d
O
O
1b
28
82
a Isolated yield.
b Reaction conditions: TBA[Fe] (1 mol%), L2 (3 mol%), KOt-Am (5 mol%),
naphthol (0.2 mmol), carbonate (0.2 mmol), EtOAc as co-solvent (0.05
mmol), MeCN (1 mL), 60 °C.
O
2c
3
91
c Reaction conditions: TBA[Fe] (5 mol%), L2 (7 mol%), KOt-Am (9 mol%),
naphthol (0.2 mmol), carbonate (0.2 mmol), THF as co-solvent (0.05
mmol), MeCN (0.5 mL), 60 °C.
d Reaction conditions: TBA[Fe] (10 mol%), L2 (12 mol%), KOt-Am (16
mol%), naphthol (0.2 mmol), carbonate (0.4 mmol), no co-solvent, MeCN
(1 mL), 100 °C.
3b
29
30
54
74
O
Despite the overall usefulness of this transformation, we
considered the rather narrow scope of allylic carbonates to
be a limitation and were wondering whether simple allyl-
oxycarbonyl-protected β-naphthols would decarboxylate in
the presence of TBA[Fe] to form the corresponding naph-
tholates. These naphtholates could then react with the al-
lyl–Fe complex to give α-allylated naphthones, to which
more complex olefinic substitution could be introduced by
employing, for example, ruthenium-catalyzed cross-meta-
thesis. We were pleased that this transformation worked
particularly well for the disubstituted β-naphthol 37 to give
the corresponding product 38 in 65% isolated yield (Scheme
2). Using monosubstituted naphthol 39 under otherwise
O
4c
Br
O
5c
31
92
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, 340–350

344
B. Heid, B. Plietker
Feature
Synthesis
identical reaction conditions led to a mixture of partially
dearomatized product 40 alongside with allyl ether 41
(Scheme 2).
0.01 mmol, 0.05 equiv) was added and the mixture was heated for 1 h
at 80 °C to coordinate the ligand. At r.t. the carbonate (0.2 mmol, 1
equiv) was added to the mixture, followed by the naphthol (0.2 mmol,
1 equiv) and the co-solvent THF (0.05 mmol). The reaction mixture
was stirred for 18 h at 60 °C. After filtration through a silica plug
(Et2O) the crude product was purified by column chromatography.
TBA[Fe] (10 mol%)
L2 (12 mol%)
KOt-Am (14 mol%)
O
1,3-Dimethyl-1-(3-methylbut-2-en-1-yl)naphthalen-2-one (3)
O
O
O
MeCN
100°C
18 h
The product was prepared according to GP I by using 1,3-dimethyl-2-
naphthol and 2-methylbut-3-en-2-yl isobutyl carbonate and ob-
tained after purification by column chromatography (silica gel, PE–
EtOAc, 20:1) as a colorless oil.
37
38
65%
Yield: 44 mg, 0.18 mmol (91%). Rf = 0.41 (PE–EtOAc, 20:1).
IR (film): 3392 (b), 3025 (w), 2970 (w), 2924 (vw), 1715 (vw), 1650
(vs), 1447 (w), 1376 (w), 1275 (w), 1061 (vw), 969 (vw), 908 (vw),
O
O
TBA[Fe] (10 mol%)
L2 (12 mol%)
KOt-Am (14 mol%)
40
28%
754 (s), 523 (vw), 462 (vw), 411 (vw) cm–1
.
O
1H NMR (300 MHz, CDCl3): δ = 7.38–7.22 (m, 5 H, ArH), 4.66–4.57 (m,
1 H, prenyl-sp2-CH), 2.80–269 (m, 1 H, prenyl-sp3-CH2), 2.47–2.37 (m,
1 H, prenyl-sp3-CH2), 1.97 (d, J = 1.3 Hz, 3 H, enone-CH3), 1.48 (s, 3 H,
prenyl-CH3), 1.45 (s, 3 H, enone-CH3), 1.39 (s, 3 H, prenyl-CH3).
+
O
O
MeCN
100°C
18 h
39
41
44%
13C NMR (75 MHz, CDCl3): δ = 204.3, 145.4, 141.3, 134.3, 132.5, 130.3,
128.5, 128.3, 126.4, 118.8, 51.4, 41.9, 25.7, 25.6, 17.7, 15.9.
Scheme 2 Intermolecular dearomatization of naphthol derivatives
GC/MS (EI, 70 eV): m/z (%) = 240 (3), 172 (100), 157 (5), 142 (6), 128
(6), 115 (2), 97 (6), 69 (10), 41 (5).
ESI-HRMS: m/z calcd for C17H20O: 240.1514; found: 240.1513.
Herein we reported an operationally simple procedure
for the allylating partial dearomatization of substituted
naphthol derivatives by using catalytic amounts of the iron
complex Bu4N[Fe(CO)3(NO)] (TBA[Fe]). Reasonable func-
tional group tolerance was observed. The obtained prod-
ucts were formed in moderate to good yields. With regard
to the usefulness of this particular reaction, future work
will focus on the development of more efficient iron-based
catalysts and the elaboration of an asymmetric version of
this transformation.
1-(2,3-Dimethylbut-2-en-1-yl)-1,3-dimethylnaphthalen-2-one
(17)
The product was prepared according to GP I by using 1,3-dimethyl-2-
naphthol and 2,3-dimethylbut-3-en-2-yl isobutyl carbonate and ob-
tained after purification by column chromatography (silica gel, PE–
EtOAc, 20:1) as a colorless oil.
Yield: 22 mg, 0.08 mmol (43%). Rf = 0.43 (PE–EtOAc, 20:1).
IR (film): 2921 (w), 2862 (w), 1717 (w), 1651 (vs), 1441 (s), 1372 (s),
1275 (w), 1263 (w), 1243 (w), 1028 (w), 967 (w), 875 (w), 754 (vs),
586 (s) cm–1
.
1H NMR (300 MHz, CDCl3): δ = 7.36–7.15 (m, 5 H, ArH), 2.83 (d, J =
13.6 Hz, 1 H, olefin-sp3-CH2), 2.53 (d, J = 13.6 Hz, 1 H, olefin- sp3-CH2),
1.97 (d, J = 1.2 Hz, 3 H, enone-CH3), 1.52 (s, 3 H, olefin-CH3), 1.45 (s, 3
H, enone-CH3), 1.35 (s, 3 H, olefin-CH3), 1.15 (s, 3 H, olefin-CH3).
13C NMR (75 MHz, CDCl3): δ = 204.4, 145.5, 140.9, 132.4, 130.2, 128.4,
128.2, 127.0, 126.4, 123.7, 52.0, 48.5, 26.9, 25.5, 20.7, 20.6, 19.5, 16.1.
Reactions which are sensitive to air or moisture were performed un-
der anhyd N2 using standard Schlenk techniques. All solvents were
purified prior to use. All chemicals were purchased from Sigma Al-
drich, Acros Organics, or Alfa Aesar. Mass spectra were measured us-
ing electronspray ionization on a Bruker Micro-TOF-Q. IR spectra
were measured on a Bruker Vector 22 FT-IR spectrometer in an ATR
mode (b = broad, w = weak, vw = very weak, s = strong, vs = very
strong). NMR spectra were recorded on a Bruker AV 300 spectrometer
(1H NMR, 300 MHz; 13C NMR, 75 MHz), a Bruker AV 250 spectrometer
(1H NMR, 250 MHz; 13C NMR, 62.5 MHz), or a Bruker AV 500 spec-
trometer (1H NMR, 500 MHz;13C NMR, 125 MHz). Chemical shifts
were reported in ppm downfield from tetramethylsilane as an inter-
nal standard.
GC/MS (EI, 70 eV): m/z (%) = 254 (1), 172 (100), 157 (5), 3), 128 (5),
115 (2), 83 (9), 55 (5).
ESI-HRMS: m/z calcd for C18H22O: 254.1671; found: 254.1676.
1,3-Dimethyl-1-(3-methyl-5-phenylpent-2-en-4-yn-1-yl)naphtha-
len-2-one (18)
The product was prepared according to GP I by using 1,3-dimethyl-2-
naphthol and isobutyl 3-methyl-5-phenylpent-1-en-4-yn-3-yl car-
bonate and obtained after purification by column chromatography
(silica gel, PE–EtOAc, 20:1) as a colorless oil.
Dearomatization of 1,3-Disubstituted Naphthols Catalyzed by the
Iron Complex Bu4N[Fe(CO)3(NO)] (TBA[Fe]); General Procedure I
(GP I)
Yield: 2.6 mg, 0.008 mmol (4%). Rf = 0.4 (PE–EtOAc, 20:1).
A 10 mL Schlenk tube was charged with L2 (4.5 mg, 0.014 mmol, 0.07
equiv) and MeCN (0.5 mL). Afterwards KOt-Am solution (1.7 M in tol-
uene, 11 μL, 0.018 mmol, 0.09 equiv) was added and the reaction
mixture was stirred for 20 min at r.t. Then Bu4N[Fe(CO)3NO] (4.2 mg,
IR (film): 2971 (w), 2920 (w), 1740 (w), 1720 (w), 1651 (s), 1488 (w),
1441 (w), 1373 (w), 1275 (w), 1260 (w), 1083 (w), 1069 (w), 1027 (s),
909 (w), 801 (w), 752 (vs), 690 (vs) cm–1
.
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B. Heid, B. Plietker
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1H NMR (300 MHz, CDCl3): δ = 7.49–7.41 (m, 3 H, ArH), 7.38–7.26 (m,
4 H, ArH), 7.25–7.20 (m, 3 H, ArH), 5.31–5.22 (m, 1 H, olefin- sp2-CH),
3.07–2.95 (m, 1 H, olefin- sp3-CH2), 2.92–2.81 (m, 1 H, olefin- sp3-
CH2), 2.00 (d, J = 1.22 Hz, 3 H, enone-CH3), 1.75 (d, J = 1.2 Hz, 3 H,
olefin-CH3), 1.49 (s, 3 H, enone-CH3).
13C NMR (75 MHz, CDCl3): δ = 141.3, 132.4, 131.1, 130.0, 128.7, 128.4,
128.2, 128.0, 126.6, 120.5, 51.5, 43.3, 26.9, 25.9, 22.9, 16.0.
1,3-Dimethyl-1-(pent-3-en-2-yl)naphthalen-2-one (21)
The product was prepared according to GP I by using 1,3-dimethyl-2-
naphthol and (E)-pent-3-en-2-yl isobutyl carbonate and obtained af-
ter purification by column chromatography (silica gel, PE–EtOAc,
20:1) as a colorless oil.
Yield: 4.8 mg, 0.02 mmol (10%). Rf = 0.51 (PE–EtOAc, 20:1).
IR (film): 2969 (w), 2928 (w), 1716 (w), 1649 (s), 1597 (vw), 1503
(vw), 1446 (s), 1373 (s), 1235 (s), 1211 (w), 1178 (s), 1102 (s), 1036
GC/MS (EI, 70 eV): m/z (%) =326 (6), 172 (21), 155 (100), 128 (7), 115
(20).
(vs), 964 (vs), 908 (s), 876 (w), 845 (w), 747 (vs), 530 (w) cm–1
.
1H NMR (300 MHz, CDCl3): δ = 7.33–7.26 (m, 2 H, ArH), 7.25–7.17 (m,
3 H, ArH), 5.40–5.26 (m, 1 H, olefin-sp2-CH), 5.26–5.13 (m, 1 H, olefin-
sp2-CH), 2.58–2.32 (m, 1 H, olefin-sp3-CH), 2.00–1.93 (m, 3 H, CH3),
1.66–1.59 (m, 3 H, CH3), 1.47–1.42 (m, 3 H, CH3), 0.78–0.66 (m, 3 H,
CH3).
13C NMR (75 MHz, CDCl3): δ = 204.8, 143.8, 141.4, 140.9, 133.4, 131.8,
131.1, 128.1, 127.8, 127.7, 126.7, 126.5, 54.1, 50.4, 49.6, 30.9, 22.4,
17.9, 15.8, 15.0.
ESI-HRMS: m/z calcd for C24H22O: 326.1671; found: 326.1664.
1-(3,7-Dimethylocta-2,6-dien-1-yl)-1,3-dimethylnaphthalen-2-
one (19)
The product was prepared according to GP I by using 1,3-dimethyl-2-
naphthol and 3,7-dimethylocta-1,6-dien-3-yl isobutyl carbonate and
obtained after purification by column chromatography (silica gel, PE–
EtOAc, 20:1) as a colorless oil.
Yield: 16 mg, 0.052 mmol (26%). Rf = 0.45 (PE–EtOAc, 20:1).
GC/MS (EI, 70 eV): m/z (%) = 240 (14), 172 (100), 157 (8), 128 (5), 69
(10), 41 (5).
IR (film): 2967 (w), 2919 (w), 2854 (w), 1650 (vs), 1441 (w), 1374
(w), 1275 (w), 1031 (w), 968 (w), 906 (w), 753 (vs) cm–1
.
ESI-HRMS: m/z calcd for C17H20O: 240.1514; found: 240.1516.
1H NMR (300 MHz, CDCl3): δ = 7.43–7.18 (m, 5 H, ArH), 5.11–4.86 (m,
1 H, olefin-sp2-CH), 4.69–4.54 (m, 1 H, olefin- sp2-CH), 2.85–2.67 (m,
1 H, olefin- sp3-CH2), 2.49–2.36 (m, 1 H, olefin-sp3-CH2), 1.97 (s, 3 H,
enone-CH3), 1.93–1.72 (m, 4 H, 2 × olefin-sp3-CH2), 1.71–1.61 (m, 3 H,
CH3), 1.54–1.47 (m, 3 H, CH3), 1.47–1.34 (m, 6 H, 2 × olefin-CH3).
13C NMR (75 MHz, CDCl3): δ = 204.3, 145.4, 141.4, 137.9, 132.6, 131.4,
131.2, 130.3, 128.5, 128.2, 126.5, 126.4, 124.3, 124.1, 118.6, 51.4, 42.2,
39.7, 26.9, 25.6, 17.5, 15.9.
1,3-Dimethyl-2-(pent-3-en-2-yloxy)naphthalene (22)
The product was prepared according to GP I by using 1,3-dimethyl-2-
naphthol and (E)-pent-3-en-2-yl isobutyl carbonate and obtained af-
ter purification by column chromatography (silica gel, PE–EtOAc,
20:1) as colorless oil.
Yield: 20.6 mg, 0.09 mmol (43%). Rf = 0.58 (PE–EtOAc, 20:1).
IR (film): 2971 (w), 2927 (w), 1650 (w), 1597 (w), 1503 (w), 1451 (s),
1372 (s), 1235 (vs), 1211 (s), 1178 (vs), 1151 (s), 1101 (vs), 1062 (s),
GC/MS (EI, 70 eV): m/z (%) = 308 (1), 172 (100), 128 (5), 81 (6), 69
(14), 41 (4).
1036 (vs), 964 (vs), 908 (vs), 876 (vs), 844 (w), 746 (vs), 530 (s) cm–1
.
1H NMR (300 MHz, CDCl3): δ = 7.89 (d, J = 8.3 Hz, 1 H, ArH), 7.70 (d, J =
8.3 Hz, 1 H, ArH), 7.49 (s, 1 H, ArH), 7.46–7.31 (m, 2 H, ArH), 5.70–
5.59 (m, 1 H, olefin- sp2-CH), 5.50–5.35 (m, 1 H, olefin-sp2-CH), 4.45–
4.32 (q, J = 6.7 Hz, 1 H, olefin- sp3-CH), 2.55 (s, 3 H, enone-CH3), 2.41
(s, 3 H, enone-CH3), 1.60 (dd, J = 1.6 Hz, J = 6.4 Hz, 3 H, olefin-CH3),
1.43 (d, J = 6.4 Hz, 3 H, olefin-CH3).
ESI-HRMS: m/z calcd for C22H28O: 308.2140; found: 308.2143.
2-[(3,7-Dimethylocta-2,6-dien-1-yl)oxy]-1,3-dimethylnaphtha-
lene (20)
The product was prepared according to GP I by using 1,3-dimethyl-2-
naphthol and 3,7-dimethylocta-1,6-dien-3-yl isobutyl carbonate and
obtained after purification by column chromatography (silica gel, PE–
EtOAc, 20:1) as a colorless oil.
13C NMR (75 MHz, CDCl3): δ = 152.6, 132.6, 132.2, 131.9, 130.6, 127.9,
127.4, 127.2, 125.0, 124.8, 124.2, 123.8, 80.2, 21.1, 18.1, 17.6, 12.8.
Yield: 2.3 mg, 0.007 mmol (4%). Rf = 0.54 (PE–EtOAc, 20:1).
GC/MS (EI, 70 eV): m/z (%) = 240 (10), 172 (100), 157 (3), 128 (6), 69
(9), 41 (4).
IR (film): 2921 (vs), 2851 (s), 1459 (w), 1376 (w), 1237 (w), 1209
(vw), 1177 (w), 1151 (vw), 1102 (w), 1062 (vw), 1028 (vw), 971 (w),
ESI-HRMS: m/z calcd for C17H20O: 240.1514; found: 240.1517.
746 (w) cm–1
.
1H NMR (300 MHz, CDCl3): δ = 7.91 (d, J = 8.1 Hz, 1 H, ArH), 7.72 (d, J =
8.1 Hz, 1 H, ArH), 7.52 (s, 1 H, ArH), 7.47–7.33 (m, 2 H, ArH), 5.71–
5.62 (m, 1 H, olefin-sp2-CH), 5.16–5.09 (m, 1 H, olefin-sp2-CH), 4.38
(d, J = 6.9 Hz, 2 H, olefin-sp3-CH2), 2.62 (s, 3 H, CH3), 2.47 (s, 3 H, CH3),
2.22–2.05 (m, 4 H, 2 × olefin-sp3-CH2), 1.70 (d, J = 3.8 Hz, 6 H, 2 × ole-
fin-CH3), 1.43 (s, 3 H, CH3).
13C NMR (75 MHz, CDCl3): δ = 154.0, 141.0, 132.5, 131.8, 131.4, 130.8,
127.5, 127.2, 124.9, 124.4, 123.8, 120.0, 69.9, 39.6, 31.9, 29.7, 26.7,
26.3, 22.3, 17.7, 17.4, 16.5, 14.1, 14.0, 11.7.
1-(But-2-en-1-yl)-1,3-dimethylnaphthalen-2-one (23)
The product was prepared according to GP I by using 1,3-dimethyl-2-
naphthol and but-3-en-2-yl isobutyl carbonate and obtained after
purification by column chromatography (silica gel, PE–EtOAc, 20:1) as
a colorless oil.
Yield: 10.3 mg, 0.045 mmol (23%). Rf = 0.38 (PE–EtOAc, 20:1).
IR (film): 3024 (vw), 2967 (w), 2920 (w), 1716 (w), 1649 (vs), 1598
(vw), 1572 (vw), 1488 (vw), 1440 (s), 1373 (s), 1272 (s), 1198 (w),
1025 (s), 966 (vs), 910 (w), 753 (vs), 566 (s), 510 (w) cm–1
.
GC/MS (EI, 70 eV): m/z (%) = 308 (1), 172 (100), 128 (5), 81 (4), 69
(11), 41 (3).
ESI-HRMS: m/z calcd for C22H28O [M + Na]+: 331.2032; found:
331.2016.
1H NMR (300 MHz, CDCl3): δ = 7.40–7.29 (m, 2 H, ArH), 7.28–7.19 (m,
3 H, ArH), 5.32–5.16 (m, 1 H, olefin-sp2-CH), 4.96–4.82 (m, 1 H, ole-
fin-sp2-CH), 2.75–2.65 (m, 1 H, olefin-sp3-CH2), 2.49–2.38 (m, 1 H,
olefin-sp3-CH2), 1.97 (d, J = 1.2 Hz, 3 H, enone-CH3), 1.49–1.36 (m, 6
H, 1 × enone-CH3, 1 × olefin-CH3).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, 340–350

346
B. Heid, B. Plietker
Feature
Synthesis
13C NMR (75 MHz, CDCl3): δ = 204.1, 145.3, 141.3, 132.5, 130.2, 128.6,
128.4, 128.3, 126.5, 126.4, 125.5, 51.4, 46.3, 26.1, 17.7, 15.8.
1H NMR (300 MHz, CDCl3): δ = 7.37–7.15 (m, 5 H, ArH), 5.41–4.97 (m,
2 H, 2 × olefin-sp2-CH), 2.57–2.32 (m, 1 H, olefin-sp3-CH), 2.00–1.96
(m, 2 H, alkyl-CH2), 1.95–1.86 (m, 3 H, CH3), 1.50–1.38 (m, 3 H, CH3),
1.31–1.17 (m, 4 H, alkyl-CH2), 0.96–0.83 (m, 3 H, CH3), 0.81–0.66 (m,
3 H, CH3).
13C NMR (75 MHz, CDCl3): δ = 204.6, 144.8, 144.0, 141.5, 141.0, 133.5,
133.4, 132.3, 131.5, 130.5, 128.1, 127.8, 127.6, 127.1, 126.5, 54.0, 50.4,
49.7, 32.2, 32.1, 31.6, 22.1, 16.3, 15.8, 15.7, 13.7.
GC/MS (EI, 70 eV): m/z (%) = 226 (15), 172 (199), 157 (6), 143 (14),
128 (13), 115 (4), 55 (6).
ESI-HRMS: m/z calcd for C16H18O: 226.1358; found: 226.1356.
2-(But-3-en-2-yloxy)-1,3-dimethylnaphthalene (24)
The product was prepared according to GP I by using 1,3-dimethyl-2-
naphthol and but-3-en-2-yl isobutyl carbonate and obtained after
purification by column chromatography (silica gel, PE–EtOAc, 20:1) as
a colorless oil.
GC/MS (EI, 70 eV): m/z (%) = 282 (8), 172 (100), 157 (5), 128 (4), 69
(11), 55 (10).
ESI-HRMS: m/z calcd for C20H26O [M + Na]+: 305.1876; found:
305.1863.
Yield: 17.6 mg, 0.08 mmol (39%). Rf = 0.51 (PE–EtOAc, 20:1).
IR (film): 3067 (w), 2975 (w), 2926 (w), 1597 (vw), 1502 (w), 1456
(w), 1420 (w), 1372 (w), 1236 (vs), 1212 (w), 1178 (s), 1152 (w), 1101
1,3-Dimethyl-2-(oct-2-en-4-yloxy)naphthalene (27)
The product was prepared according to GP I by using 1,3-dimethyl-2-
naphthol and isobutyl oct-2-en-4-yl carbonate and obtained after pu-
rification by column chromatography (silica gel, PE–EtOAc, 20:1) as a
colorless oil.
(vs), 1047 (s), 989 (s), 918 (s), 878 (s), 845 (w), 746 (vs), 530 (s) cm–1
.
1H NMR (300 MHz, CDCl3): δ = 7.89 (d, J = 8.0 Hz, 1 H, ArH), 7.70 (d, J =
8.0 Hz, 1 H, ArH), 7.50 (s, 1 H, ArH), 7.47–7.32 (m, 2 H, ArH), 6.10–
5.93 (m, 1 H, olefin-sp2-CH), 5.15–5.03 (m, 2 H, olefin-sp2-CH2), 4.52–
4.40 (q, J = 6.5 Hz, 1 H, olefin-sp3-CH), 2.57 (s, 3 H, enone-CH3), 2.43
(s, 3 H, enone-CH3), 1.44 (dd, J = 5.3 Hz, J = 6.4 Hz, 3 H, olefin-CH3).
13C NMR (75 MHz, CDCl3): δ = 152.5, 139.1, 132.6, 131.7, 130.7, 127.4,
127.3, 124.9, 124.3, 123.8, 116.2, 80.3, 20.8, 18.1, 12.9.
Yield: 18.2 mg, 0.06 mmol (32%). Rf = 0.45 (PE–EtOAc, 20:1).
1H NMR (300 MHz, CDCl3): δ = 7.89 (d, J = 8.2 Hz, 1 H, ArH), 7.70 (d, J =
8.2 Hz, 1 H, ArH), 7.48 (s, 1 H, ArH), 7.45–7.31 (m, 2 H, ArH), 5.65–
5.46 (m, 1 H, olefin-sp2-CH), 5.44–5.21 (m, 1 H, olefin-sp2-CH), 4.46–
4.35 (m, 1 H, olefin-sp3-CH), 2.56 (s, 3 H, enone-CH3), 2.46 (s, 3 H,
enone-CH3), 1.93 (q, J = 6.4 Hz, 2 H, olefin-CH2), 1.45 (d, J = 6.4 Hz, 3 H,
olefin-CH3), 1.26–1.07 (m, 4 H, 2 × alkyl-CH2), 0.77 (t, J = 7.3 Hz, 3 H,
alkyl-CH3).
GC/MS (EI, 70 eV): m/z (%) = 226 (15), 172 (100), 157 (5), 143 (6), 128
(13), 115 (3), 55 (3).
ESI-HRMS: m/z calcd for C16H18O: 226.1358; found: 226.1355.
13C NMR (75 MHz, CDCl3): δ = 152.6, 133.5, 132.6, 131.8, 130.6, 127.4,
127.1, 125.0, 124.8, 124.2, 123.8, 80.3, 31.7, 30.9, 22.0, 21.2, 18.1,
17.6, 13.8, 12.8.
1,3-Dimethyl-1-(3-methyl-4-phenylbut-2-en-1-yl)naphthalen-2-
one (25)
The product was prepared according to GP I by using 1,3-dimethyl-2-
naphthol and isobutyl 2-methyl-1-phenylbut-3-en-2-yl carbonate
and obtained after purification by column chromatography (silica gel,
PE–EtOAc, 20:1) as a colorless oil.
IR (film): 2955 (w), 2926 (w), 2858 (w), 1651 (w), 1502 (w), 1455 (s),
1374 (s), 1235 (vs), 1211 (w), 1178 (w), 1151 (w), 1102 (s), 1037 (s),
967 (s), 915 (w), 844 (w), 745 (vs), 529 (s) cm–1
.
GC/MS (EI, 70 eV): m/z (%) = 282 (1), 172 (100), 157 (6), 128 (8), 69
(12), 55 (10).
Yield: 6.8 mg, 0.02 mmol (11%). Rf = 0.55 (PE–EtOAc, 20:1).
IR (film): 3060 (vw), 3024 (vw), 2974 (w), 2917 (w), 1648 (vs), 1599
(vw), 1572 (vw), 1492 (w), 1450 (s), 1374 (s), 1275 (w), 1028 (s), 755
ESI-HRMS: m/z calcd for C20H26O [M + Na]+: 305.1876; found:
305.1873.
(vs), 732 (vs), 698 (vs) cm–1
.
1H NMR (300 MHz, CDCl3): δ = 7.40–7.26 (m, 3 H, ArH), 7.25–7.09 (m,
5 H, ArH), 7.04–6.80 (m, 2 H, ArH), 4.83–4.66 (m, 1 H, olefin-sp2-CH),
3.04 (s, 2 H, benzyl-CH2), 2.89–2.76 (m, 1 H, olefin-sp3-CH2), 2.55–
2.45 (m, 1 H, olefin-sp3-CH2), 1.93 (m, 3 H, enone-CH3), 1.48 (s, 3 H,
olefin-CH3), 1.31 (m, 3 H, enone-CH3).
13C NMR (75 MHz, CDCl3): δ = 204.2, 145.4, 141.7, 139.9, 136.9, 132.6,
128.6, 128.5, 128.3, 128.2, 128.0, 126.5, 125.7, 121.0, 51.3, 46.0, 42.4,
26.1, 15.9.
1-Hexyl-3-methyl-1-(3-methylbut-2-en-1-yl)naphthalen-2-one
(30)
The product was prepared according to GP I by using 1-hexyl-3-
methyl-2-naphthol and 2-methylbut-3-en-2-yl isobutyl carbonate
and obtained after purification by column chromatography (silica gel,
PE–EtOAc, 20:1) as a colorless oil.
Yield: 45.7 mg, 0.15 mmol (74%). Rf = 0.51 (PE–EtOAc, 20:1).
IR (film): 3023 (vw), 2954 (s), 2855 (w), 1714 (vw), 1649 (vs), 1441
(s), 1376 (s), 1273 (w), 1196 (w), 1109 (vw), 976 (w), 947 (w), 909
GC/MS (EI, 70 eV): m/z (%) = 316 (5), 172 (100), 145 (13), 128 (4), 91
(5).
ESI-HRMS: m/z calcd for C23H24O [M + Na]+: 339.1719; found:
339.1712.
(w), 753 (vs) cm–1
.
1H NMR (300 MHz, CDCl3): δ = 7.35–7.27 (m, 2 H, ArH), 7.25–7.18 (m,
3 H, ArH), 4.60–4.50 (m, 1 H, prenyl-sp2-CH), 2.81–2.70 (m, 1 H, pre-
nyl-sp3-CH2), 2.48–2.35 (m, 1 H, prenyl-sp3-CH2), 2.29–2.14 (m, 1 H,
alkyl-CH2), 1.95 (d, J = 1.4 Hz, 3 H, enone-CH3), 1.87–1.73 (m, 1 H, al-
kyl-CH2), 1.44 (s, 3 H, prenyl-CH3), 1.37 (s, 3 H, prenyl-CH3), 1.22–0.99
(m, 6 H, 3 × alkyl-CH2), 0.85–0.65 (m, 5 H, alkyl-CH2 + alkyl-CH3).
13C NMR (75 MHz, CDCl3): δ = 204.3, 144.3, 141.6, 133.9, 133.4, 131.5,
128.5, 128.2, 126.4, 126.3, 118.4, 55.9, 42.5, 41.6, 31.4, 29.6, 25.6,
24.5, 22.5, 17.7, 15.7, 13.9.
1,3-Dimethyl-1-(oct-3-en-2-yl)naphthalen-2-one (26)
The product was prepared according to GP I by using 1,3-dimethyl-2-
naphthol and isobutyl oct-2-en-4-yl carbonate and obtained after pu-
rification by column chromatography (silica gel, PE–EtOAc, 20:1) as a
colorless oil.
Yield: 10.3 mg, 0.036 mmol (18%). Rf = 0.40 (PE–EtOAc, 20:1).
IR (film): 2957 (w), 2925 (w), 2871 (w), 1649 (vs), 1453 (s), 1375 (s),
GC/MS (ESI): m/z (%) = 333 [M + Na+].
1236 (w), 1102 (vw), 1029 (vw), 965 (s), 907 (w), 752 (vs) cm–1
.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, 340–350

347
B. Heid, B. Plietker
Feature
Synthesis
ESI-HRMS: m/z calcd for C22H30O [M + Na]+: 333.2189, found:
333.2172.
1H NMR (300 MHz, CDCl3): δ = 7.51–7.45 (m, 3 H, ArH), 7.44–7.27 (m,
7 H, ArH), 4.80–4.72 (m, 1 H, prenyl-sp2-CH), 2.86–2.76 (m, 1 H, pre-
nyl-sp3-CH2), 2.54–2.44 (m, 1 H, prenyl-sp3-CH2), 1.55 (s, 3 H, CH3),
1.51 (s, 3 H, CH3), 1.40 (s, 3 H, CH3).
13C NMR (75 MHz, CDCl3): δ = 202.6, 145.7, 142.0, 136.1, 135.4, 134.6,
130.2, 129.5, 129.3, 128.6, 128.1, 127.9, 126.7, 126.5, 118.7, 52.6, 42.2,
25.7, 24.9, 17.8.
3-Bromo-1-methyl-1-(3-methylbut-2-en-1-yl)naphthalen-2-one
(31)
The product was prepared according to GP I by using 3-bromo-1-
methyl-2-naphthol and 2-methylbut-3-en-2-yl isobutyl carbonate
and obtained after purification by column chromatography (silica gel,
PE–EtOAc, 20:1) as a colorless oil.
GC/MS (EI, 70 eV): m/z (%) = 302 (1), 287 (3), 234 (100), 205 (5), 69
(6).
C22H22O [M +
H]+: 303.1743; found:
Yield: 55.8 mg, 0.18 mmol (92%). Rf = 0.18 (PE–EtOAc, 20:1).
ESI-HRMS: m/z calcd for
303.1728.
IR (film): 2975 (w), 2927 (w), 1734 (w), 1672 (vs), 1608 (w), 1415
(w), 1375 (w), 1347 (w), 1260 (w), 1224 (w), 756 (s) cm–1
.
1H NMR (300 MHz, CDCl3): δ = 7.87 (s, 1 H, ArH), 7.46–7.36 (m, 2 H,
ArH), 7.33–7.36 (m, 2 H, ArH), 4.67–4.57 (m, 1 H, prenyl-sp2-CH),
2.85–2.74 (m, 1 H, prenyl-sp3-CH2), 2.50–2.40 (m, 1 H, prenyl-sp3-
CH2), 1.53 (s, 3 H, enone-CH3), 1.50 (s, 3 H, prenyl-CH3), 1.39 (s, 3 H,
prenyl-CH3).
13C NMR (75 MHz, CDCl3): δ = 196.6, 146.3, 145.3, 135.4, 130.0, 129.9,
128.9, 127.0, 126.8, 122.1, 117.8, 53.9, 42.5, 25.9, 25.6, 17.7.
Dearomatization of 1-Substituted Naphthols Catalyzed by the Iron
Complex Bu4N[Fe(CO)3(NO)] (TBA[Fe]); General Procedure II (GP II)
A 10 mL Schlenk tube was charged with L2 (2.1 mg, 0.006 mmol, 0.03
equiv) and MeCN (1 mL). Afterwards KOt-Am solution (1.7 M in tolu-
ene, 6 μL, 0.01 mmol, 0.05 equiv) was added and the reaction mixture
was stirred for 20 min at r.t. Then Bu4N[Fe(CO)3NO] (1.1 mg, 0.002
mmol, 0.01 equiv) was added and the mixture was heated for 1 h at
80 °C to coordinate the ligand. At r.t. the carbonate (0.2 mmol, 1
equiv) was added to the mixture, followed by the naphthol (0.2
mmol, 1 equiv) and the co-solvent EtOAc (0.05 mmol). The reaction
mixture was stirred for 18 h at 60 °C. After filtration through a silica
plug (Et2O), the crude product was purified by column chromatogra-
phy.
GC/MS (EI, 70 eV): m/z (%) = 304 (5), 261 (4), 250 (11), 236 (100), 143
(8), 128 (25), 69 (28), 41 (16).
ESI-HRMS: m/z calcd for C16H17BrO: 304.0463, 306.0444; found:
304.0455, 306.0439.
3-Iodo-1-methyl-1-(3-methylbut-2-en-1-yl)naphthalen-2-one
(32)
1-Methyl-1-(3-methyl-5-phenylpent-2-en-1-yl)naphthalen-2-one
(13)
The product was prepared according to GP I by using 3-iodo-1-meth-
yl-2-naphthol and 2-methylbut-3-en-2-yl isobutyl carbonate and ob-
tained after purification by column chromatography (silica gel, PE–
EtOAc, 8:1) as a colorless oil.
The product was prepared according to GP II by using 1-methyl-2-
naphthol and isobutyl 3-methyl-5-phenylpent-1-en-3-yl carbonate
and obtained after purification by column chromatography (silica gel,
PE–EtOAc, 20:1) as a colorless oil.
Yield: 46.2 mg, 0.13 mmol (66%). Rf = 0.63 (PE–EtOAc, 8:1).
Yield: 34.3 mg, 0.10 mmol (54%). Rf = 0.28 (PE–EtOAc, 20:1).
IR (film) ν 3062 (w), 2970 (w), 2927 (w), 2910 (w), 1665 (vs), 1602
(w), 1555 (w), 1449 (w), 1344 (w), 1300 (w), 1222 (w), 915 (w), 834
IR (film): 3061 (vw), 3025 (vw), 2970 (vw), 2929 (vw), 1655 (vs),
1620 (vw), 1599 (vw), 1564 (w), 1494 (w), 1452 (w), 1396 (w), 834
(w), 754 (vs), 575 (w) cm–1
.
(w), 755 (s), 699 (s) cm–1
.
1H NMR (300 MHz, CDCl3): δ = 8.17 (s, 1 H, ArH), 7.46–7.37 (m, 2 H,
ArH), 7.31–7.21 (m, 2 H, ArH), 4.65–4.56 (m, 1 H, prenyl-sp2-CH),
2.82–2.71 (m, 1 H, prenyl-sp3-CH2), 2.47–2.36 (m, 1 H, prenyl-sp3-
CH2), 1.53 (s, 3 H, enone-CH3), 1.50 (s, 3 H, prenyl-CH3), 1.39 (s, 3 H,
prenyl-CH3).
1H NMR (300 MHz, CDCl3): δ = 7.43–727 (m, 6 H, ArH), 7.25–7.11 (m,
3 H, ArH), 7.08–7.02 (m, 1 H, ArH), 6.16–6.13 (dd, J = 2.9 Hz, J = 9.8 Hz,
1 H, ArH), 4.74–4.60 (m, 1 H, olefin-sp2-CH), 2.81–2.69 (m, 1 H, ole-
fin-sp3-CH2), 2.57–2.31 (m, 2 H, CH2), 2.25–2.03 (m, 1 H, olefin-sp3-
CH2), 1.52 (d, J = 1.3 Hz, 2 H, CH2), 1.47–1.40 (m, 6 H, 2 × CH3).
13C NMR (75 MHz, CDCl3): δ = 197.7, 153.9, 145.8, 135.3, 131.0, 130.2,
13C NMR (75 MHz, CDCl3): δ = 204.3, 144.8, 142.2, 129.8, 129.2, 128.3,
128.2, 126.8, 126.7, 126.6, 125.7, 125.6, 125.3, 119.1, 51.8, 41.7, 41.4,
34.5, 34.0, 33.8, 25.4, 23.3, 16.2.
128.7, 126.8, 117.9, 101.8, 52.8, 42.7, 34.1, 25.9, 25.7, 17.8.
GC/MS (EI, 70 eV): m/z (%) = 352 (4), 298 (3), 284 (100), 128 (9), 69
(8), 41 (3).
GC/MS (EI, 70 eV): m/z (%) = 316 (9), 173 (3), 158 (100), 128 (5), 91
(27), 55 (1).
ESI-HRMS: m/z calcd for C16H17IO: 352.0324; found: 352.0327.
ESI-HRMS: m/z calcd for C23H24O [M + Na]+: 339.1711; found:
339.1719.
1-Methyl-1-(3-methylbut-2-en-1-yl)-3-phenylnaphthalen-2-one
(33)
The product was prepared according to GP I by using 1-methyl-3-
phenyl-2-naphthol and 2-methylbut-3-en-2-yl isobutyl carbonate
and obtained after purification by column chromatography (silica gel,
PE–EtOAc, 20:1) as a colorless oil.
1-(2,3-Dimethylbut-2-en-1-yl)-1-methylnaphthalen-2-one (14)
The product was prepared according to GP II by using 1-methyl-2-
naphthol and 2,3-dimethylbut-3-en-2-yl isobutyl carbonate and ob-
tained after purification by column chromatography (silica gel, PE–
EtOAc, 20:1) as a colorless oil.
Yield: 39.4 mg, 0.13 mmol (65%). Rf = 0.45 (PE–EtOAc, 20:1).
IR (film): 3055 (w), 3024 (w), 2969 (w), 2912 (w), 1655 (vs), 1619
(w), 1597 (w), 1490 (w), 1447 (s), 1373 (s), 1358 (s), 1292 (s), 1210
(w), 1157 (w), 1076 (vw), 910 (vw), 755 (vs), 710 (s), 694 (vs), 578
Yield: 6 mg, 0.025 mmol (12%). Rf = 0.32 (PE–EtOAc, 20:1).
IR (film): 2961 (w), 2924 (w), 1720 (w), 1260 (s), 1085 (s), 1018 (vs),
(w), 509 (w) cm–1
.
798 (vs) cm–1
.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, 340–350

348
B. Heid, B. Plietker
Feature
Synthesis
1H NMR (300 MHz, CDCl3): δ = 7.40–7.31 (m, 3 H, ArH), 7.30–7.24 (m,
2 H, ArH), 6.15 (d, J = 9.8 Hz, 1 H, ArH), 2.87 (d, J = 13.6 Hz, 1 H, olefin-
sp3-CH2), 2.57 (d, J = 1 Hz, 1 H, olefin-sp3-CH2), 1.52 (s, 3 H, CH3), 1.46
(s, 3 H, CH3), 1.37 (s, 3 H, CH3), 1.18 (s, 3 H, CH3).
13C NMR (75 MHz, CDCl3): δ = 204.4, 146.0, 144.3, 129.6, 129.3, 129.2,
128.7, 127.2, 126.5, 125.2, 123.6, 52.4, 47.8, 25.6, 20.7, 20.6, 19.5.
IR (film): 3306 (w), 2969 (w), 2912 (w), 1652 (vs), 1564 (w), 1448
(w), 1396 (vw), 1375 (vw), 1229 (vw), 1239 (vw), 1207 (vw), 835 (s),
755 (vs) cm–1
.
1H NMR (300 MHz, CDCl3): δ = 7.43–7.35 (m, 3 H, ArH), 7.33–7.27 (m,
2 H, ArH), 6.14 (d, J = 9.9 Hz, 1 H, ArH), 4.69–4.60 (m, 1 H, prenyl-sp2-
CH), 2.82–2.72 (m, 1 H, prenyl-sp3-CH2), 2.50–2.39 (m, 1 H, prenyl-
sp3-CH2), 1.49 (s, 3 H, CH3), 1.46 (s, 3 H, CH3), 1.40 (s, 3 H, CH3).
13C NMR (75 MHz, CDCl3): δ = 204.3, 146.1, 144.9, 134.5, 129.8, 129.7,
129.3, 126.7, 126.5, 125.2, 118.6, 51.8, 41.6, 25.7, 25.6, 17.7.
GC/MS (EI, 70 eV): m/z (%) = 240 (7), 158 (100), 128 (6), 83 (9), 55 (6).
ESI-HRMS: m/z calcd for C17H20O: 240.1514; found: 240.1521.
GC/MS (EI, 70 eV): m/z (%) = 226 (13), 211 (5), 195 (2), 181 (4), 165
(1), 158 (100), 141 (3), 128 (14), 115 (4), 83 (1), 69 (11), 41 (9).
2-[(2,3-Dimethylbut-3-en-2-yl)oxy]-1-methylnaphthalene (15)
The product was prepared according to GP II by using 1-methyl-2-
naphthol and 2,3-dimethylbut-3-en-2-yl isobutyl carbonate and ob-
tained after purification by column chromatography (silica gel, PE–
EtOAc, 20:1) as a colorless oil.
ESI-HRMS: m/z calcd for C16H18O: 226.1352; found: 226.1364.
1-Hexyl-1-(3-methylbut-2-en-1-yl)naphthalen-2-one (29)
Yield: 30.5 mg, 0.13 mmol (63%). Rf = 0.64 (PE–EtOAc, 20:1).
The product was prepared according to GP II by using 1-hexyl-2-
naphthol and 2-methylbut-3-en-2-yl isobutyl carbonate and ob-
tained after purification by column chromatography (silica gel, PE–
EtOAc, 20:1) as a colorless oil.
IR (film): 3402 (b), 2974 (s), 2864 (w), 1719 (vs), 1594 (w), 1509 (w),
1466 (s), 1376 (s), 1244 (s), 1132 (s), 1082 (s), 901 (w), 831 (w), 810
(w), 755 (s), 528 (w) cm–1
.
Yield: 32.4 mg, 0.11 mmol (54%). Rf = 0.43 (PE–EtOAc, 20:1).
1H NMR (300 MHz, CDCl3): δ = 7.94 (d, J = 8.5 Hz, 1 H, ArH), 7.75 (d, J =
8.0 Hz, 1 H, ArH), 7.54 (d, J = 9.1 Hz, 1 H, ArH), 7.50–7.43 (m, 1 H,
ArH), 7.37–7.30 (m, 1 H, ArH), 7.27 (d, J = 9.2 Hz, 1 H, ArH), 5.02 (s, 1
H, olefin-sp2-CH2), 4.99–4.96 (m, 1 H, olefin-sp2-CH2), 2.57 (s, 3 H,
enone-CH3), 1.97 (s, 3 H, CH3), 1.49 (s, 6 H, 2 × CH3).
13C NMR (75 MHz, CDCl3): δ = 251.1, 129.5, 128.1, 126.0, 125.7, 123.7,
123.5, 120.2, 110.8, 81.4, 27.1, 19.1, 11.6.
IR (film): 2955 (w), 2924 (s), 2855 (w), 1654 (vs), 1621 (w), 1564 (w),
1450 (w), 1396 (vw), 1377 (vw), 1236 (w), 827 (s), 755 (vs) cm–1
.
1H NMR (300 MHz, CDCl3): δ = 7.43–7.38 (m, 3 H, ArH), 7.33–7.26 (m,
2 H, ArH), 6.15 (d, J = 9.9 Hz, 1 H, ArH), 4.63–4.53 (m, 1 H, prenyl-sp2-
CH), 2.83–2.72 (m, 1 H, prenyl-sp3-CH2), 2.49–2.37 (m, 1 H, prenyl-
sp3-CH2), 2.19–2.25 (m, 1 H, alkyl-CH2), 1.90–1.77 (m, 1 H, alkyl-CH2),
1.44 (s, 3 H, prenyl-CH3), 1.38 (s, 3 H, prenyl-CH3), 1.23–1.00 (m, 6 H,
3 × alkyl-CH2), 0.97–0.83 (m, 2 H, alkyl-CH2), 0.78 (t, J = 7.3 Hz, 3 H,
alkyl-CH3).
13C NMR (75 MHz, CDCl3): δ = 204.5, 145.1, 145.0, 134.2, 131.0, 129.7,
129.2, 126.6, 126.4, 126.2, 118.2, 56.2, 42.4, 41.7, 31.4, 29.6, 25.6,
24.4, 22.5, 17.7, 13.9.
GC/MS (EI, 70 eV): m/z (%) = 241 (6), 171 (100), 157 (78), 143 (48),
128 (10), 99 (6).
ESI-HRMS: m/z calcd for
C17H20O [M +
H]+: 241.1589; found:
241.1587.
1-(But-2-en-1-yl)-1-methylnaphthalen-2-one (16)
GC/MS (EI, 70 eV): m/z (%) = 297 (100), 241 (60), 229 (5), 213 (6), 171
(6), 157 (12), 145 (3).
The product was prepared according to GP II by using 1-methyl-2-
naphthol and but-3-en-2-yl isobutyl carbonate and obtained after
purification by column chromatography (silica gel, PE–EtOAc, 20:1) as
a colorless oil.
ESI-HRMS: m/z calcd for
C21H28O [M +
H]+: 297.2213; found:
297.2223.
Yield: 6.2 mg, 0.027 mmol (14%). Rf = 0.32 (PE–EtOAc, 20:1).
Dearomatization of 6-Substituted Naphthols Catalyzed by the Iron
Complex Bu4N[Fe(CO)3(NO)] (TBA[Fe]); General Procedure III (GP
III)
IR (film): 3025 (w), 2968 (w), 2931 (w), 1719 (vw), 1652 (vs), 1620
(w), 1596 (vw), 1564 (w), 1448 (w), 1396 (w), 1375 (vw), 1298 (vw),
1238 (w), 1207 (w), 966 (s), 834 (s), 755 (vs) cm–1
.
A 10 mL Schlenk tube was charged with L2 (8.0 mg, 0.024 mmol, 0.12
equiv) and MeCN (1 mL). Afterwards KOt-Am solution (1.7 M in tolu-
ene, 19 μL, 0.032 mmol, 0.16 equiv) was added and the reaction mix-
ture was stirred for 20 min at r.t. Then Bu4N[Fe(CO)3NO] (8.2 mg, 0.02
mmol, 0.1 equiv) was added and the mixture was heated for 1 h at 80
°C to coordinate the ligand. At r.t. the carbonate (0.4 mmol, 2 equiv)
was added to the mixture, followed by the naphthol (0.2 mmol, 1
equiv). The reaction mixture was stirred for 18 h at 100 °C. After fil-
tration through a silica plug (Et2O), the crude product was purified by
column chromatography.
1H NMR (300 MHz, CDCl3): δ = 7.44–7.36 (m, 3 H, ArH), 7.34–7.27 (m,
2 H, ArH), 6.14 (d, J = 9.8 Hz, 1 H, ArH), 5.32–5.18 (m, 1 H, olefin-sp2-
CH), 5.00–4.85 (m, 1 H, olefin-sp2-CH), 2.80–2.68 (m, 1 H, olefin-sp3-
CH2), 2.51–2.41 (m, 1 H, olefin-sp3-CH2), 1.46–1.40 (m, 6 H, 2 × CH3).
13C NMR (75 MHz, CDCl3): δ = 204.1, 146.0, 144.9, 129.8, 129.7, 129.3,
128.6, 126.7, 126.6, 125.3, 125.2, 51.8, 45.9, 26.2, 17.8.
GC/MS (EI, 70 eV): m/z (%) = 212 (16), 158 (100), 129 (11), 55 (7).
ESI-HRMS: m/z calcd for C15H16O [M + Na]+: 235.1093; found:
235.1079.
6-Methyl-1,1-bis(3-methylbut-2-en-1-yl)naphthalen-2-one (34)
The product was prepared according to GP III by using 6-methyl-2-
naphthol and 2-methylbut-3-en-2-yl isobutyl carbonate and ob-
tained after purification by column chromatography (silica gel, PE–
EtOAc, 20:1) as a colorless oil.
1-Methyl-1-(3-methylbut-2-en-1-yl)naphthalen-2-one (28)
The product was prepared according to GP II by using 1-methyl-2-
naphthol and 2-methylbut-3-en-2-yl isobutyl carbonate and ob-
tained after purification by column chromatography (silica gel, PE–
EtOAc, 20:1) as a colorless oil.
Yield: 47.1 mg, 0.16 mmol (80%). Rf = 0.39 (PE–EtOAc, 20:1).
Yield: 37.1 mg, 0.16 mmol (82%). Rf = 0.28 (PE–EtOAc, 20:1).
IR (film): 2968 (w), 2912 (w), 2857 (vw), 1652 (vs), 1564 (w), 1438
(s), 1376 (s), 1219 (w), 824 (vs) cm–1
.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, 340–350

349
B. Heid, B. Plietker
Feature
Synthesis
1H NMR (300 MHz, CDCl3): δ = 7.35–7.26 (m, 2 H, ArH), 7.22–7.16 (m,
1 H, ArH), 7.09 (s, 1 H, ArH), 6.09 (d, J = 9.83 Hz, 1 H, ArH), 4.62–4.52
(m, 2 H, 2 × prenyl-sp2-CH), 2.91–2.78 (m, 2 H, 2 × prenyl-sp3-CH2),
2.52–2.41 (m, 2 H, 2 × prenyl-sp3-CH2), 2.37 (s, 3 H, CH3), 1.45 (s, 12 H,
4 × prenyl-CH3).
13C NMR (75 MHz, CDCl3): δ = 204.3, 145.1, 140.6, 135.9, 133.9, 130.8,
130.4, 129.7, 126.9, 126.0, 118.7, 56.0, 40.4, 26.9, 25.6, 20.8, 17.9.
Intramolecular Dearomatization Catalyzed by the Iron Complex
Bu4N[Fe(CO)3(NO)] (TBA[Fe]); General Procedure VII (GP VII)
A 10 mL Schlenk tube was charged with L2 (8.0 mg, 0.024 mmol, 0.12
equiv) and MeCN (1 mL). Afterwards KOt-Am solution (1.7 M in tolu-
ene, 16 μL, 0.028 mmol, 0.14 equiv) was added and the reaction mix-
ture was stirred for 20 min at r.t. Then Bu4N[Fe(CO)3NO] (8.2 mg, 0.02
mmol, 0.1 equiv) was added and the mixture was heated for 1 h at 80
°C to coordinate the ligand. At r.t. the naphthol (0.2 mmol, 1 equiv)
was added. The reaction mixture was stirred for 18 h at 100 °C. After
filtration through a silica plug (Et2O), the crude product was purified
by column chromatography.
GC/MS (EI, 70 eV): m/z (%) = 294 (11), 226 (80), 209 (7), 183 (12), 171
(100), 141 (5), 69 (14), 41 (10).
ESI-HRMS: m/z calcd for C21H26O [M + Na]+: 317.1876; found:
317.1878.
1-Allyl-1,3-dimethylnaphthalen-2-one (38)
6-Bromo-1,1-bis(3-methylbut-2-en-1-yl)naphthalen-2-one (35)
The product was prepared according to GP VII by using allyl 1,3-di-
methyl-2-naphthyl carbonate and obtained after purification by col-
umn chromatography (silica gel, PE–EtOAc, 20:1) as a colorless oil.
The product was prepared according to GP III by using 6-bromo-2-
naphthol and 2-methylbut-3-en-2-yl isobutyl carbonate and ob-
tained after purification by column chromatography (silica gel, PE–
EtOAc, 20:1) as a colorless oil.
Yield: 27.5 mg, 0.13 mmol (65%). Rf = 0.43 (PE–EtOAc, 20:1).
IR (film): 3070 (vw), 2976 (vw), 2922 (vw), 1649 (vs), 1438 (w), 1371
(w), 1275 (w), 1199 (vw), 1026 (w), 992 (w), 912 (s), 754 (vs), 738 (s),
Yield: 51.5 mg, 0.14 mmol (72%). Rf = 0.43 (PE–EtOAc, 20:1).
IR (film): 2968 (w), 2911 (w), 2856 (vw), 1655 (vs), 1586 (vw), 1551
(w), 1482 (w), 1489 (s), 1375 (s), 1320 (vw), 1288 (vw), 1231 (s),
1198 (s), 1121 (vw), 1105 (vw), 1082 (w), 873 (s), 819 (vs), 686 (w),
657 (vw), 631 (vw), 494 (w) cm–1
.
1H NMR (300 MHz, CDCl3): δ = 7.41–7.29 (m, 2 H, ArH), 7.26–7.21 (m,
3 H, ArH), 5–34–5.19 (m, 1 H, allyl-sp2-CH), 4.86–4.74 (m, 2 H, allyl-
sp3-CH2), 2.87–2.77 (m, 1 H, allyl-sp3-CH2), 2.58–2.48 (m, 1 H, allyl-
sp3-CH2), 1.98 (d, J = 1.3 Hz, 3 H, enone-CH3), 1.45 (s, 3 H, enone-CH3).
13C NMR (75 MHz, CDCl3): δ = 203.7, 145.0, 141.5, 133.2, 132.5, 130.2,
128.7, 128.5, 126.6, 126.4, 117.6, 51.1, 47.1, 26.7, 15.8.
581 (w), 555 (w), 460 (w) cm–1
.
1H NMR (300 MHz, CDCl3): δ = 7.49 (dd, J = 2.2 Hz, J = 8.3 Hz, 1 H,
ArH), 7.42 (d, J = 2.2 Hz, 1 H, ArH), 7.30–7.24 (m, 2 H, ArH), 6.14 (d, J =
9.8 Hz, 1 H, ArH), 4.60–4.50 (m, 2 H, 2 × prenyl-sp2-CH), 2.92–2.78 (m,
2 H, 2 × prenyl-sp3-CH2), 2.53–2.38 (m, 2 H, 2 × prenyl-sp3-CH2), 1.45
(d, J = 7.0 Hz, 12 H, 4 × prenyl-CH3).
GC/MS (EI, 70 eV): m/z (%) = 212 (51), 197 (5), 171 (100), 143 (56),
128 (45), 115 (14).
ESI-HRMS: m/z calcd for C15H16O [M + Na]+: 235.1092; found:
13C NMR (75 MHz, CDCl3): δ = 203.3, 143.4, 143.3, 134.5, 132.9, 132.1,
131.6, 128.8, 127.1, 120.1, 118.1, 56.3, 40.3, 25.6, 17.9.
235.1105.
GC/MS (EI, 70 eV): m/z (%) = 358 (15), 290 (98), 235 (100), 195 (40),
168 (24), 152 (9), 128 (9), 83 (7), 69 (62), 41 (26).
ESI-HRMS: m/z calcd for C20H23BrO [M + Na]+: 381.0824, 383.0806;
1-Allyl-1-methylnaphthalen-2-one (40)
The product was prepared according to GP VII by using allyl 1-meth-
yl-2-naphthyl carbonate and obtained after purification by column
chromatography (silica gel, PE–EtOAc, 20:1) as a colorless oil.
found: 381.0822, 383.0806.
tert-Butyl 5,5-Bis(3-methylbut-2-en-1-yl)-6-oxo-5,6-dihy-
dronaphthalene-2-carboxylate (36)
Yield: 10.8 mg, 0.06 mmol (28%). Rf = 0.25 (PE–EtOAc, 20:1).
IR (film): 2974 (vw), 1716 (vw), 1655 (vw), 952 (s), 835 (vw), 757
The product was prepared according to GP III by using 6-tert-butoxy-
carbonyl-2-naphthol and 2-methylbut-3-en-2-yl isobutyl carbonate
and obtained after purification by column chromatography (silica gel,
PE–EtOAc, 10:1) as a colorless oil.
(vw), 707 (vs), 676 (vs) cm–1
.
1H NMR (300 MHz, CDCl3): δ = 7.48–7.38 (m, 3 H, ArH), 7.34–7.27 (m,
2 H, ArH), 6.16 (d, J = 10.0 Hz, 1 H, ArH), 5.39–5.22 (m, 1 H, allyl-sp2-
CH), 4.88–4.75 (m, 2 H, allyl-sp3-CH2), 2.90–2.80 (m, 1 H, allyl-sp3-
CH2), 2.60–2.50 (m, 1 H, allyl-sp3-CH2), 1.46 (s, 3 H, enone-CH3).
13C NMR (75 MHz, CDCl3): δ = 203.7, 145.7, 145.0, 133.0, 129.9, 129.7,
129.4, 126.76, 126.72, 125.2, 117.9, 51.5, 46.7, 26.7.
Yield: 11.5 mg, 0.03 mmol (19%). Rf = 0.72 (PE–EtOAc, 10:1).
IR (film): 2973 (w), 2928 (w), 1713 (vs), 1658 (vs), 1624 (w), 1452
(w), 1368 (s), 1293 (vs), 1256 (w), 1229 (s), 1203 (vw), 1162 (vs),
1125 (s), 1107 (s), 916 (vw), 848 (w), 827 (w), 761 (w) cm–1
.
1H NMR (300 MHz, CDCl3): δ = 7.99 (dd, J = 6.4 Hz, J = 8.2 Hz, 1 H,
ArH), 7.90 (d, J = 1.8 Hz, 1 H, ArH), 7.48–7.39 (m, 2 H, ArH), 6.17 (d, J =
9.9 Hz, 1 H, ArH), 4.58–4.49 (m, 2 H, 2 × prenyl-sp2-CH), 2.95–2.84 (m,
2 H, 2 × prenyl-sp3-CH2), 2.58–2.44 (m, 2 H, 2 × prenyl-sp3-CH2), 1.62
(s, 9 H, tBu-CH3), 1.44 (s, 12 H, 4 × prenyl-CH3).
GC/MS (EI, 70 eV): m/z (%) = 198 (84), 183 (8), 170 (23), 157 (100),
143 (53), 129 (67), 115 (12).
ESI-HRMS: m/z calcd for C14H14O [M + Na]+: 221.0937; found:
221.0932.
13C NMR (75 MHz, CDCl3): δ = 203.4, 165.1, 149.3, 144.3, 134.5, 131.0,
130.4, 130.1, 130.0, 127.1, 126.7, 118.1, 81.4, 56.7, 40.5, 28.2, 25.6,
17.9.
2-(Allyloxy)-1-methylnaphthalene (41)
The product was prepared according to GP VII by using allyl 1-meth-
yl-2-naphthyl carbonate and obtained after purification by column
chromatography (silica gel, PE–EtOAc, 20:1) as a colorless oil.
GC/MS (EI, 70 eV): m/z (%) =380 (15), 312 (40), 256 (97), 239 (19), 201
(100), 69 (27), 57 (12), 41 (22).
ESI-HRMS: m/z calcd for C25H32O3 [M + Na]+: 403.2244, found:
Yield: 17.4 mg, 0.09 mmol (44%). Rf = 0.49 (PE–EtOAc, 20:1).
403.2245.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, 340–350

350
B. Heid, B. Plietker
Feature
Synthesis
IR (film): 2921 (vw), 2862 (vw), 1624 (w), 1594 (w), 1510 (w), 1468
(w), 1382 (vw), 1337 (vw), 1261 (s), 1243 (vs), 1218 (vs), 1180 (vw),
1147 (w), 1087 (s), 1020 (s), 989 (s), 920 (s), 799 (vs), 769 (s), 742
References
(1) (a) Roche, S. P.; Porco, J. A. Jr. Angew. Chem. Int. Ed. 2011, 50,
4068. (b) Zhuo, C.-X.; Zhang, W.; You, S.-L. Angew. Chem. Int. Ed.
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(g) Zheng, J.; Wang, S.-B.; Zheng, C.; You, S.-L. J. Am. Chem. Soc.
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4179.
(vs), 701 (w), 522 (w), 416 (w) cm–1
.
1H NMR (300 MHz, CDCl3): δ = 7.95 (d, J = 8.8 Hz, 1 H, ArH), 7.77 (d, J =
8.2 Hz, 1 H, ArH), 7.68 (d, J = 9.1 Hz, 1 H, ArH), 7.52–7.43 (m, 1 H,
ArH), 7.40–7.30 (m, 1 H, ArH), 7.22 (d, J = 8.9 Hz, 1 H, ArH), 6.19–6.03
(m, 1 H, allyl-sp2-CH), 5.51–5.23 (m, 2 H, allyl-sp3-CH2), 4.65 (dt, J =
1.5 Hz, 5.3 Hz, 2 H, allyl-sp2-CH2), 2.58 (s, 3 H, enone-CH3).
13C NMR (75 MHz, CDCl3): δ = 153.4, 133.8, 133.7, 129.2, 128.3, 127.0,
126.0, 123.5, 123.4, 120.1, 117.1, 115.4, 70.5, 10.7.
GC/MS (EI, 70 eV): m/z (%) = 198 (92), 157 (100), 129 (38).
ESI-HRMS: m/z calcd for C14H14O: 198.1045; found: 198.1047.
(2) (a) Biber, N.; Möws, K.; Plietker, B. Nat. Chem. 2011, 3, 938.
(b) Lindermayr, K.; Plietker, B. Angew. Chem. Int. Ed. 2013, 52,
12183. (c) Horeischi, F.; Biber, N.; Plietker, B. J. Am. Chem. Soc.
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21, 3053. (e) Horeischi, F.; Guttroff, C.; Plietker, B. Chem.
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2010, 132, 13642. (b) Grenning, A. J.; Boyce, J. H.; Porco, J. A. Jr
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Acknowledgment
Financial support by the Deutsche Forschungsgemeinschaft and the
Ministerium für Wissenschaft und Kultur (Cluster BW2, Ph.D-grant for
B.H.) is gratefully acknowledged.
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Supporting Information
Supporting information for this article is available online at
http://dx.doi.org/10.1055/s-0035-1560909.
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