Pd-catalysed domino arylation/CH activation for the synthesis of acenaphthylenes

Article abstract of DOI:10.1002/ejoc.200600428

The palladium-catalysed domino cyclisation of the aryl bromides 4, containing an alkyne and a bromonaphthyl moiety, leads to tetracycles of type 5 in good yields. The substrates 4 are easily accessible by addition of the corresponding lithiated alkynes 7

Full text of DOI:10.1002/ejoc.200600428

FULL PAPER
DOI: 10.1002/ejoc.200600428
Pd-Catalysed Domino Arylation/CH Activation for the Synthesis of
Acenaphthylenes
Lutz F. Tietze*[a] and Florian Lotz[a]
Keywords: Acenaphthylenes / Alkynes / CH activation / Domino reactions / Oxacyclopentaphenanthrenes / Palladium
catalysis / Pyrans
The palladium-catalysed domino cyclisation of the aryl bro-
mides 4, containing an alkyne and a bromonaphthyl moiety,
leads to tetracycles of type 5 in good yields. The substrates
4 are easily accessible by addition of the corresponding lithi-
ated alkynes 7 to the aldehyde 6.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2006)
However, by using 4a as substrate the expected alkene 3
was not obtained but the acenaphthylene 5a (Scheme 2).
Introduction
The development of highly efficient synthetic procedures
towards complex molecules is an important aim in modern
preparative organic chemistry. One way to improve effi-
ciency is the use of domino reactions.[1] Some time ago, we
have developed a domino-Heck reaction for the synthesis of
tetra-substituted sterically hindered alkenes such as 2 using
compounds of type 1 as substrates (Scheme 1).[2] The reac-
tions proceed with excellent selectivity and high yields.
Moreover, a multitude of ring-size analogues have been pre-
pared. The obtained sterically hindered alkenes are of great
interest as molecular switches as well as for the design of
molecular motors.[3]
Scheme 2. Pd-catalysed transformation of 4a.
Here we describe the scope and limitation of this new
procedure using different substrates of type 4, namely 4a–k
and their Pd-catalysed transformations to give the acenaph-
thylenes 5a–h.
Scheme 1. Palladium-catalysed domino cyclisation of 1 for the syn-
thesis of sterically hindered alkenes.
In order to enlarge the scope of this transformation and
prepare more rigid compounds it was our intention to em-
ploy an aromatic moiety instead of the allylic silane as ter-
minating acceptor group in the domino process, where the
desired final C–C bond would be formed by a CH acti-
vation.[4]
Results and Discussion
The substrates 4a–k for the twofold palladium-catalysed
process to give the acenaphthylenes 5a–h were synthesised
in high yields of usually over 84% by addition of the lithi-
ated alkynes 7a–k to the (bromonaphthyloxy)acetaldehyde
6 at –60 °C in THF (Scheme 3). Only 7d and 7g had slightly
lower yields (65% and 76%, respectively). It should be
noted that the alkyne has usually to be employed in a two-
[a] Institut für Organische und Biomolekulare Chemie der Georg-
August-Universität Göttingen,
Tammannstraße 2, 37077 Göttingen, Germany
Fax: +49-551-399476
E-mail: ltietze@gwdg.de
4676
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2006, 4676–4684

Pd-Catalysed Synthesis of Acenaphthylenes
FULL PAPER
Scheme 3. Synthesis of the substrates 4a–k from 6 and 7a–k as well as Pd-catalysed formation of the acenaphthylenes 5a–h: a) nBuLi,
THF, –60 °C, room temp., –60 °C; b) LiOAc, Bu4NOAc, CH3CN/DMF/H2O (5:5:1), Herrmann–Beller catalyst 14.
fold excess to give good results; the excess alkyne can easily
be recovered by chromatography after the transformation.
Thus, reaction of 6 with 1.2 equiv. of 7k afforded 4k in only
24% yield whereas with 2.0 equiv. of 7k the product was
obtained in 92% yield. However, in some cases as in the
reaction of 6 with 7a and 7h 1.2 equiv. were sufficient to
give high yields; in the first of the two transformations an
addition of LiBr was favourable.
Scheme 5. Synthesis of the arylalkyne 7a: a) HCl, H2O, NaNO2,
The (bromonaphthyloxy)acetaldehyde 6 was either ob-
0 °C, 40 min; b) KI, –5 °C, 2 h; c) room temp.Ǟ45 °CǞ80 °C; d)
iPr2NH, Pd(PPh3)2Cl2, CuI, 18 h, room temp.; e) MnO2, KOH,
Et2O, 1 h, room temp.
tained by alkylation of the commercially available bromo-
naphthol 9 with 2-bromoethanol followed by an oxidation
of the formed 8 with Dess–Martin periodinane[5] or by alky-
lation of 9 with allyl bromide to give 10 which was trans-
formed into 6 by ozonolysis (Scheme 4).
The domino reactions of 4a–k were performed using
catalytic amounts of the Herrmann–Beller palladacycle
14[6,7] (10 mol-%, Scheme 6) at 120–140 °C in a solvent mix-
ture of DMF/CH3CN/H2O (5:5:1). The best results were
obtained employing the aromatic alkynes 4a–4g, which led
to the desired acenaphthylenes 5a–g in 69–98% yield
(Scheme 3). Notably, the hydroxy group does not have to
be protected in these transformations. Aliphatic alkynes can
also be used; however, with much lower yield. Thus, reac-
tion of 4h led to 5h in only 37% yield. On the other hand,
sterically hindered aliphatic alkynes such as 4i and the tri-
methylsilyl alkyne 4k did not give any of the desired prod-
Scheme 4. Synthesis of the aldehyde 6 from bromonaphthol 9: a)
NaH, DMF, room temp., 15 h at 50 °C, 78%; b) CH2Cl2, DMP,
20 h room temp., 79%; c) K2CO3, acetone, reflux overnight, 81%;
d) O3, CH2Cl2, –78 °C, 9 min, Me2S, –78 °CǞ20 °C, 49 %.
The alkynes 7b–k are commercially available. On the uct. Using 4i as substrate only the first Pd-catalysed C–C
other hand these alkynes can also be prepared using a pro- bond formation took place to give 15 in 33% yield
cedure which we have developed for the synthesis of alkyne (Scheme 6). In the reaction of 4k decomposition was ob-
7a. This compound was obtained from the commercially served only.
available arylamine 11 by treatment with NaNO2 and KI
In addition to the use of the palladacene 14 several other
to form the corresponding iodo compound 12, which was Pd0 compounds like Pd(OAc)2 and Pd2(dba)3 were em-
used in a Pd-catalysed coupling with propargylic alcohol ployed in the transformation in the presence and absence of
under Sonogashira conditions to give the propargylic HP(tBu)3BF4. However, in none of these reactions the de-
alcohol 13 followed by oxidation with MnO2 (Scheme 5).
sired products 5a–k were obtained employing even harsh
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L. F. Tietze, F. Lotz
FULL PAPER
with those obtained from the product of 4c where a forma-
tion of products such as 3 is not possible clearly indicated
that both (5a and 5c) have the same structural core. Thus,
the UV spectra of 5a and 5c are nearly identical with a λmax
at 378.0 nm and 380.0 nm, respectively. The signals in the
13C NMR spectra for the oxacyclopenta[def]phenanthrene
moiety in 5a and 5c are again nearly identical. Moreover,
2-H2 and 3-H of 5a resonate at δ = 4.62 and δ = 4.44 with
J = 11.7 Hz and a centred multiplett at δ = 5.26 ppm. For
1
the same hydrogen atoms signals are observed in the H
NMR spectrum of 5c at δ = 4.72 as well as δ = 4.39 with J
= 12.0 Hz and a centred multiplett at δ = 5.09 ppm.
As a mechanism for the formation of 5 from 4 we pro-
pose the following (Scheme 7). In the first step an oxidative
addition of 4 to give 17 takes place which then undergoes
an insertion into the triple bond to form a vinyl-Pd species
18 as an intermediate. This undergoes a CH activation via
the transition state 19 to give 20, which leads to 5 in a
reductive elimination. This mechanism also allows to ex-
plain that compound 3 is not formed starting from 4a be-
cause a transition structure as 21 would be of higher energy
than 19 due to its greater flexibility. This proposal for CH
activation is in agreement with recent publications.[10] One
could argue that by changing the substituent pattern at the
aromatic ether system a reversed selectivity could be in-
duced. However, as shown by Echavarren in CH activation
of aromatic compounds, electron-donating and -with-
drawing groups have nearly the same effect on the reaction
rate. This finding is clearly incompatible with an electro-
philic substitution mechanism where the electron density of
the substituents would have a great influence. We therefore
focus in our approach towards the synthesis of compounds
of type 3 on a blocking of the position C-8 in 4a with a
methyl group or the use of a tetraline derivative, because
the CH activation of an aliphatic compound should be less
feasible, though it was recently shown that even that is pos-
sible.[11]
Scheme 6. Palladacene 14 and the products 15 and 16.
conditions with reaction temperatures up to 170 °C. Due to
the failure with these catalysts and the unlikeliness of a
PdII/PdIV process using the palladacene 14, we assume that
in the formation of 5a–h nanoparticles of Pd are formed
from 14. However, the use of preformed nanoparticles[8] sta-
bilised with a tenside did not give any transformation.[9]
The products 5 were obtained as racemic mixtures, be-
cause the substrates 4 were used as racemic mixtures. How-
ever, one can easily perform a resolution of the substrates
4 as well as of the products 5 using HPLC on a chiral sta-
tionary phase.
The acenaphthylenes 5a–h tend to undergo an elimi-
nation of water to form a pyran moiety, which for 5a and
5b already took place upon standing in CDCl3 at room tem-
perature for some hours to give 16a and 16b, respectively
(Scheme 6).
The structures of the new compounds were determined
by NMR and mass spectroscopy. At the beginning, the
structural differentiation between 5a and 3 was not an easy
task, as both compounds have the same mass and contain
one aryl–H less than the substrate 4a. However, comparison
of the spectroscopic data of the cyclisation product of 4a
Scheme 7. Proposed mechanism of the Pd-catalysed domino reaction of 4 to give 5.
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Eur. J. Org. Chem. 2006, 4676–4684

Pd-Catalysed Synthesis of Acenaphthylenes
FULL PAPER
solvent in vacuo, water was given to the residue and the mixture
extracted with Et2O. The organic layer was washed with 5% NaOH
solution, water and brine, dried (MgSO4) and the solvent was re-
moved in vacuo. Purification by flash chromatography gave 10 as
a colourless solid (11.5 g, 81%). Rf = 0.55 (pentane/Et2O, 20:1). 1H
NMR (600 MHz, CDCl3): δ = 8.21 (d, J = 8.0 Hz, 1 H, 8-H), 7.74–
7.79 (m, 2 H, 3-H, 5-H), 7.55 (mc, 1 H, 7-H), 7.38 (mc, 1 H, 6-H),
7.23 (d, J = 8.9 Hz, 1 H, 3-H), 6.11 (ddt, J = 17.4, 10.7, 5.0 Hz, 1
H, 2Ј-H), 5.51 (dq, J = 17.3, 1.5 Hz, 1 H, 3Ј-Htrans), 5.31 (dq, J =
10.7, 1.5 Hz, 1 H, 3Ј-Hcis), 4.75 (dt, J = 5.0, 1.5 Hz, 2 H, 1Ј-H)
ppm. 13C NMR (50.3 MHz, CDCl3): δ = 152.9 (C-2), 133.1 (C-8a),
132.8 (C-2Ј), 130.0 (C-4a), 128.8 (C-4), 128.0 (C-5), 127.6 (C-7),
126.2 (C-8), 124.4 (C-6), 117.9 (C-3Ј), 115.3 (C-3), 109.6 (C-1),
Conclusions
The palladium-catalysed cyclisation of substrates of type
4 containing an alkyne and a bromonaphthyl moiety per-
mits a highly efficient and regioselective synthesis of the
acenaphthylenes 5a–h in a domino fashion. The yields of
the process and the reactivity of the substrates mainly de-
pend on the substituent R at the triple bond in 4, whereas
the compounds containing an aryl substituent gave the best
results. The products can be obtained in an enantiopure
form, since the substrates and products can be easily re-
solved on a chiral stationary phase (HPLC).
70.61 (C-1Ј) ppm. IR (KBr): ν = 3376 (OH), 2987, 2928 (CH),
˜
1622 (C=C cm–1). UV (CH3CN): λmax (lgε) = 335 (3.3916), 322.5
(3.3333), 294.5 (3.7041), 282.5 (3.7718), 273.0 (3.6486), 232.0 nm
(4.8681). MS (70 eV, EI): m/z (%) = 264 (46) [M]+, 223.0 (28)
[C10H6BrO]+, 183.1 (36) [M – Br]+. C13H11BrO (263.13): calcd.
C 59.34, H 4.21; found C 59.26, H 4.08.
Experimental Section
General: All reactions were performed under argon in flame-dried
flasks and the reactants were introduced by syringe. All solvents
were dried by standard methods. Solvents used in Pd-catalysed re-
actions were degassed by pump and freeze methodology. All rea-
gents obtained from commercial sources were used without further
purification. Thin-layer chromatography was performed on pre-
coated silica gel plates (SIL G/UV254, Macherey–Nagel GmbH &
Co. KG). Silica gel 60 (0.032–0.064 mm) (Merck) was used for col-
umn chromatography. Ozone: Fischer Ozone generator model 502
(flow: 3 g O3 per hour). UV/Vis spectra (CH3CN): Mettler Lambda
2 spectrometer. IR spectra (KBr pellets or films): Bruker Vector 22
spectrometer. 1H and 13C NMR spectra: Varian Mercury 200, Var-
ian Mercury 300, Unity 300 or Inova 600 spectrometer with tet-
ramethylsilane (TMS) as the internal standard in [D]chloroform or
[D6]benzene. Mass spectra (70 eV): Finnigan MAT95. Analytical
HPLC: Jasco, with AS-2055 Plus Sampler, DG-1580-54 Degasser,
LG-1580-04 mixing chamber, PU-2080 Plus Pump and a MD-2010
Plus Multiwave Detector. Resolution: Chiracel OD (Diacel Chemi-
cal Industries): Solvents 2-propanol and n-hexane (Acros).
2-(1-Bromonaphth-2-yloxy)acetaldehyde (6). Method A: A solution
of 2-(1-bromonaphthyl-2-yloxy)ethanol (8) (1.00 g, 3.74 mmol) in
CH2Cl2 (40 mL) was treated with Dess–Martin periodinane (2.38 g,
5.62 mmol) in one portion and stirred for 20 h at room temp. The
reaction was quenched by addition of saturated aqueous solution
of NaHCO3 and 1  Na2S2O3, and the mixture was stirred for 1 h.
After extraction with CH2Cl2, washing with brine and drying over
MgSO4 the solvent was evaporated in vacuo and the residue puri-
fied by flash chromatography to give 6 as colourless solid (780 mg,
2.94 mmol, 79%). Method B: A solution of 1-bromo-2-(prop-2-en-
yloxy)naphthalene (10) (1.00 g, 3.80 mmol) in dry CH2Cl2 (20 mL)
was treated with O3 (9 min, 0.05 A, O2 stream: 50 mbar) by using
a glass pipe. The reaction was finished by bubbling N2 for 5 min
through the solution and addition of SMe2 (3.8 mL). After removal
of the solvent in vacuo the residue was taken up in CH2Cl2 (20 mL)
and washed with brine and dried (MgSO4). The solvent was re-
moved in vacuo and the obtained crude product purified by flash
chromatography to give 6 as a colourless solid (494 mg, 49%). Rf
= 0.41 (CH2Cl2). 1H NMR (300 MHz, CDCl3): δ = 9.96 (t, J =
1.1 Hz, 1 H, 1-H), 8.24 (mc, 1 H, 8Ј-H), 7.76–7.82 (m, 2 H, 4Ј-H,
5Ј-H), 7.58 (mc, 1 H, 7Ј-H), 7.43 (mc, 1 H, 6Ј-H), 7.10 (d, J =
9.0 Hz, 1 H, 3Ј-H), 4.73 (d, J = 1.1 Hz, 2 H, 2-H2) ppm. 13C NMR
(50.3 MHz, CDCl3): δ = 198.9 (C-1), 152.2 (C-2Ј), 133.1 (C-8Јa),
130.5 (C-4Јa), 129.2 (C-4Ј), 128.0, 128.1 (C-7Ј, C-5Ј), 126.4 (C-8Ј),
125.1 (C-6Ј), 115.2 (C-3Ј), 110.4 (C-1Ј), 74.80 (C-2) ppm. IR (KBr):
2-(1-Bromonaphth-2-yloxy)ethanol (8): NaH (60% in paraffin,
468 mg, 11.7 mmol) was added to a stirred solution of 1-bromo-2-
naphthol (9) (2.01 g, 9.00 mmol) in DMF (25 mL) at room temp.
After the formation of gas had ceased, 2-bromoethanol (3.37 g,
1.92 mL, 27.0 mmol) was added and stirring was continued at
50 °C for 15 h. Water was added, and the mixture extracted with
Et2O. The organic phases were washed with brine, dried with
MgSO4 and the solvent removed in vacuo. Purification of the resi-
due by flash chromatography yielded 8 as a colourless solid (1.87 g,
ν = 2924, 2832, 2717 (C–H), 1729 (C=O cm–1). UV (CH CN): λ
˜
3
max
1
78%). Rf = 0.53 (pentane/ethyl acetate, 1:1). H NMR (300 MHz,
(lgε) = 333.5 (3.342), 321.0 (3.280), 294.5 (3.701), 282.5 (3.767),
231.0 nm (4.830). MS (200 eV, DCI): m/z (%) = 548.1 (14) [2M +
NH4]+, 299.1 (100) [M + NH3 + NH4]+, 282.0 (53) [M + NH4]+.
C12H9BrO2 (265.10): calcd. C 54.37, H 3.42; found: C 54.17, H
3.25.
CDCl3): δ = 8.22 (d, J = 8.6 Hz, 1 H, 8Ј-H), 7.81 (d, J = 8.9 Hz, 1
H, 4Ј-H), 7.79 (d, J = 8.2 Hz, 1 H, 5Ј-H), 7.58 (ddd, J = 8.3, 6.9,
1.3 Hz, 1 H, 7Ј-H), 7.42 (ddd, J = 8.3, 6.9, 1.5 Hz, 1 H, 6Ј-H), 7.26
(d, J = 8.9 Hz, 1 H, 3Ј-H), 4.30 (t, J = 4.3 Hz, 2 H, 2-H2), 4.03 (t, J
= 4.3 Hz, 2 H, 1-H2), 2.37 (s, 1 H, OH) ppm. 13C NMR (50.3 MHz,
CDCl3): δ = 152.8 (C-2Ј), 133.0 (C-4Јa), 130.2 (C-8Јa), 129.0 (C-
4Ј), 128.0 (C-5Ј), 127.8 (C-7Ј), 124.7 (C-6Ј), 115.6 (C-3Ј), 110.1 (C-
1-Iodo-2-phenoxybenzene (12): A solution of 2-phenoxyaniline (11)
(9.26 g, 50.0 mmol) in 50 mL water and 15 mL concd. HCl was
treated with a solution of NaNO2 (3.60 g, 52.2 mmol) in 10 mL
water at 0 °C for 40 min. The reaction mixture was transferred
within 2 h into a KI solution (8.60 g, 52.0 mmol) in 15 mL water
at –5 °C. The formed orange suspension was stirred at room temp.
(5 min), at 45 °C (15 min) and at 80 °C (15 min). After cooling
down to 0 °C 25 mL of an aqueous 1  Na2S2O3 solution was
added, and the mixture was extracted with ethyl acetate. The or-
ganic layer was washed with brine, the solvent removed in vacuo,
1Ј), 71.90 (C-2), 61.40 (C-1) ppm. IR (KBr): ν = 3214 (OH), 2873
˜
(C–H), 1451 (CH2),1269 (Ar–O), 1058 (CH2–O) cm–1. UV
(CH3CN): λmax (lgε) = 335.0 (3.372), 323.0 (3.329), 294.5 (3.696),
282.5 (3.767), 231.0 nm (4.832). MS (ESI): m/z (%) = 289.1 (100)
[M + Na]+, 291.0 (92) [M + Na]+. C12H11BrO2 (267.12): calcd. C
53.96, H 4.15; found C 53.91, H 4.12.
1-Bromo-2-(prop-2-enyloxy)naphthalene (10):
A mixture of 1-
bromo-2-naphthol (9) (12.0 g, 53.8 mmol), allyl bromide (9.12 g, and the crude product purified by flash chromatography to give 12
75.4 mmol) and K2CO3 (11.9 g, 86.0 mmol) in dry acetone
(100 mL) was refluxed under argon for 18 h. After removal of the
as a colourless solid (9.91 g, 67%). Rf = 0.49 (pentane/ethyl acetate,
100:1). 1H NMR (300 MHz, CDCl3): δ = 7.86 (dd, J = 7.8, 1.5 Hz,
Eur. J. Org. Chem. 2006, 4676–4684
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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4679

L. F. Tietze, F. Lotz
FULL PAPER
1 H, 6-H), 7.25–7.39 (m, 3 H, 4-H, 3Ј-H, 5Ј-H), 7.13 (tt, J = 7.4, 1-(1-Bromonaphth-2-yloxy)-4-(2-phenoxyphenyl)but-3-yn-2-ol (4a):
1.3 Hz, 1 H, 4Ј-H), 6.97–7.02 (m, 2 H, 2Ј-H, 6Ј-H), 6.84–6.93 (m, Reaction of aldehyde 6 (500 mg, 1.89 mmol) and alkyne 7a
2 H, 5-H, 3-H) ppm. 13C NMR (50.3 MHz, CDCl3): δ = 156.8 (C- (439 mg, 2.26 mmol) with LiBr (197 mg, 2.26 mmol) according to
1Ј), 156.4 (C-2), 139.8 (C-6), 129.8 (C-3Ј, C-5Ј), 129.6 (C-4), 125.3 general procedure II afforded 4a (781 mg, 90%) as a colourless
(C-5), 123.4 (C-4Ј), 119.4 (C-3), 118.4 (C-2Ј, C-6Ј), 88.90 (C-1) solid after column chromatography. Rf = 0.14 (pentane/ethyl ace-
1
ppm. IR (KBr): ν = 3051 (C–H), 1228 (Ar–O) cm–1. UV (CH CN): tate, 10:1). H NMR (300 MHz, CDCl3): δ = 8.20 (d, J = 8.7 Hz,
˜
3
λmax (lgε) = 276.5 (3.318), 269.5 nm (3.322). MS (70 eV, EI): m/z 1 H, 8Ј-H), 7.78 (d, J = 7.9 Hz, 1 H, 4Ј-H), 7.76 (d, J = 8.9 Hz, 1
(%) = 296.0 (100) [M]+, 169.1 (57) [M – I]+, 141.1 (32) [M – H, 5Ј-H), 7.56 (ddd, J = 7.0, 5.5, 1.5 Hz, 1 H, 7Ј-H), 7.48 (dd, J =
CIO]+, 115.0 (16) [M – C3H2IO]. C12H9IO (296.10): calcd. C 48.67,
H 3.06; found C 48.79, H 2.89.
7.6, 1.5 Hz, 1 H, 6ЈЈ-H), 7.41 (ddd, J = 8.3, 7.0, 1.3 Hz, 1 H, 6Ј-
H), 7.22–7.32 (m, 3 H, 4ЈЈ-H, 3ЈЈЈ-H, 5ЈЈЈ-H), 7.18 (d, J = 9.0 Hz,
1 H, 3Ј-H), 6.12–7.12 (m, 5 H, 3ЈЈ-H, 5ЈЈ-H, 2ЈЈЈ-H, 4ЈЈЈ-H, 6ЈЈЈ-
H), 4.95 (ddd, J = 7.6, 4.9, 3.4 Hz, 1 H, 2-H), 4.18 (dd, J = 9.8,
3.4 Hz, 1 H, 1-Ha), 4.09 (dd, J = 9.8, 7.6 Hz, 1 H, 1-Hb), 3.77 (d,
J = 4.9 Hz, 1 H, OH) ppm. 13C NMR (75.5 MHz, CDCl3): δ =
157.4, 157.3 (C-2ЈЈ, C-1ЈЈЈ), 152.6 (C-2Ј), 133.9 (C-4ЈЈ), 133.0 (C-
8Јa), 130.3 (C-4Јa), 130.2 (C-6ЈЈ), 129.6 (C-3ЈЈЈ, C-5ЈЈЈ), 129.0 (C-
4Ј), 128.0, 127.8 (C-5Ј, C-7Ј), 126.3 (C-8Ј), 124.8 (C-6Ј), 123.6 (C-
5ЈЈ), 123.0 (C-4ЈЈЈ), 119.5 (C-3ЈЈ), 118.2 (C-2ЈЈЈ, C-6ЈЈЈ), 116.0 (C-
3Ј), 114.7 (C-1ЈЈ), 110.4 (C-1Ј), 90.73 (C-3), 82.03 (C-4), 73.88 (C-
General Procedure I
Alkynylation of Aryl Iodides: Propargylic alcohol (12.0 mmol),
bis(triphenylphosphane)palladium dichloride (0.08 mmol) and cop-
per(I) iodide (0.16 mmol) were added to a magnetically stirred solu-
tion of the aryl iodide (4.0 mmol) in iPr2NH (10 mL). The solution
was carefully heated to 30–40 °C (1 min) until the yellow suspen-
sion got dark green/brown. After stirring for the stated time at
room temp. the reaction mixture was poured into 40 mL of Et2O,
passed through a small layer of silica gel which was washed with
Et2O and the solvent was removed in vacuo. The crude product
was dissolved in Et2O (25 mL). Activated MnO2 (40 mmol) and
KOH (20 mmol) were added and the mixture stirred for 1 h at room
temp. The reaction mixture was again filtered through a small layer
of silica gel which was washed with Et2O. The residue was purified
by column chromatography after evaporation of the solvent.
4), 73.88 (C-1), 61.96 (C-1) ppm. IR (KBr): ν = 3555 (OH), 2925
˜
(C–H), 1486, 1442 (CH2), 1221 (O–Ar) cm–1. UV (CH3CN): λmax
(lgε) = 335.5 (3.270), 322.0 (3.253), 292.5 (3.855), 282.5 (3.918),
271.5 (3.844), 231.0 nm (4.935). MS (70 eV, EI): m/z (%) = 458.3
(4) [M]+, 379.2 (4) [M – Br]+, 361.2 (100) [M – HOBr]+, 222.0 (20)
[C16H14O]+. C26H19BrO3 (459.33): calcd. C 67.99, H 4.17; found C
67.72, H 3.91.
1-(1-Bromonaphth-2-yloxy)-4-(4-methoxybenzene)but-3-yn-2-ol
(4b): Reaction of aldehyde 6 (250 mg, 0.943 mmol) and alkyne 7b
(249.3 mg, 1.89 mmol) according to general procedure II afforded
4b (313 mg, 84%) as a light green/yellow solid after column
1-Ethinyl-2-phenyloxybenzene (7a): Reaction of aryl iodide 12
(1.18 g, 4.00 mmol), iPr2NH (10 mL), propargylic alcohol (675 mg,
0.710 mL, 12.0 mmol), bis(triphenylphosphane)palladium dichlo-
ride (56.2 mg, 0.080 mmol) and copper(I) iodide (30.5 mg,
0.16 mmol) [crude product Rf = 0.10 (pentane/Et2O, 3:1)] followed
by treatment of activated MnO2 (3.48 g, 40.0 mmol) and potassium
hydroxide (1.12 g, 20.0 mmol) was performed according to the ge-
neral procedure I. Column chromatography (pentane/Et2O, 10:1)
afforded 7a (544 mg, 70% over two steps) as a colourless solid. Rf
chromatography. Rf
=
0.19 (pentane/Et2O, 2:1). 1H NMR
(300 MHz, CDCl3): δ = 8.20 (d, J = 8.6 Hz, 1 H, 8Ј-H), 7.74–7.80
(m, 2 H, 4Ј-H, 5Ј-H), 7.57 (ddd, J = 8.6, 7.0, 1.3 Hz, 1 H, 7Ј-H),
7.41 (ddd, J = 8.2, 7.0, 1.1 Hz, 1 H, 6Ј-H), 7.36 (mc, 2 H, 2ЈЈ-H,
6ЈЈ-H), 7.26 (d, J = 9.0 Hz, 1 H, 3Ј-H), 6.80 (mc, 2 H, 3ЈЈ-H, 5ЈЈ-
H), 5.45 (dd, J = 7.3, 3.4 Hz, 1 H, 2-H), 4.42 (dd, J = 9.6, 3.4 Hz,
1 H, 1-Ha), 4.31 (dd, J = 9.6, 7.3 Hz, 1 H, 1-Hb), 3.77 (s, 3 H,
OMe), 3.05 (br. s, 1 H, OH) ppm. 13C NMR (75.5 MHz, CDCl3):
δ = 159.9 (C-4ЈЈ), 152.6 (C-2Ј), 133.3 (C-2ЈЈ, C-6ЈЈ), 133.0 (C-8Јa),
130.4 (C-4Јa), 129.1 (C-4Ј), 128.1 (C-5Ј), 127.8 (C-7Ј), 126.3 (C-8Ј),
124.9 (C-6Ј), 116.1 (C-3Ј), 114.1 (C-1ЈЈ), 113.9 (C-3ЈЈ, C-5ЈЈ), 110.5
(C-1Ј), 86.3 (C-3), 84.2 (C-4), 74.32 (C-1), 62.07 (C-2), 55.24 (C–
1
= 0.22 (pentane). H NMR (300 MHz, CDCl3): δ = 7.54 (dd, J =
7.9, 1.9 Hz, 1 H, 6-H), 7.24–7.37 (m, 3 H, 4-H, 3Ј-H, 5Ј-H), 7.11
(tt, J = 7.4, 1.3 Hz, 1 H, 4Ј-H), 6.99–7.07 (m, 3 H, 3-H, 2Ј-H, 6Ј-
H), 6.86 (dd, J = 8.3, 1.1 Hz, 1 H, 5-H), 3.22 (s, 1 H, 2ЈЈ-H) ppm.
13C NMR (50.3 MHz, CDCl3): δ = 158.4 (C-1Ј), 156.9 (C-2), 134.3
(C-4), 130.2 (C-6), 129.7 (C-5Ј, C-3Ј), 123.5 (C-5), 123.2 (C-4Ј),
118.9 (C-2Ј, C-6Ј), 118.5 (C-3), 114.3 (C-1), 81.70 (C-2ЈЈ), 79.30 (C-
OMe) ppm. IR (KBr): ν = 3374 (OH), 2929 (C–H), 1246 (O–Ar)
˜
1ЈЈ) ppm. IR (KBr): ν = 3283 (C –H), 3054 (Ar–H), 1477 (CH ),
˜
sp
2
cm–1. UV (CH3CN): λmax (lgε) = 334.0 (3.335), 322.0 (3.296), 293.5
(3.789), 282.0 (3.930), 252.0 (4.490), 231.0 (4.868), 204.5 nm
(4.606). MS (70 eV, EI): m/z (%) = 396.1 (3) [M]+, 317.2 (100) [M –
Br]+, 222.0 (28) [C10H6BrO]+, 181.1 (77) [C13H9O]+, 161.1 (52)
[C10H9O2]+, 126.1 (17) [C10H6]+. HRMS (EI): 396.0361.
C21H17BrO3 [M]+ requires 396.0361. C21H17BrO3 (397.26): calcd.
C 63.49, H 4.31; found C 63.35, H 4.06.
1236 (Ar–O). UV (CH3CN): λmax (lgε)
=
297.0 (3.233),
278.0 (3.240), 288.0 (3.313), 270.5 nm (3.181) cm–1. MS (70 eV, EI):
m/z (%) = 194.2 (54) [M]+, 168.1 (24) [M – C2H2]+, 165.2 (56) [M –
CHO]+, 77.1 (34) [C6H5]+. C14H10O (194.23): calcd. C 86.57, H
5.19; found C 86.80, H 4.89.
General Procedure II
Addition of Lithiated Alkynes to Aldehydes: nBuLi (2.5  in hexane,
1-(1-Bromonaphth-2-yloxy)-4-phenylbut-3-yn-2-ol (4c): Reaction of
0.80 mL, 2.0 mmol) was added to a stirred solution of the alkyne
aldehyde 6 (200 mg, 0.754 mmol) and alkyne 7c (154 mg,
(2.0 mmol) in THF (2 mL) at –60 °C and the reaction mixture was 1.51 mmol) according to general procedure II afforded 4c (248 mg,
allowed to reach room temp. within 1 h. After cooling again to
–60 °C, a solution of the aldehyde (1.0 mmol) in THF (2.5 mL) was
added dropwise at –60 °C with a transfer cannula, and the mixture
was stirred for 30 min. Stirring was continued at –45 °C for 30 min
and 1 h at room temp. An aqueous saturated NH4Cl solution
(2 mL) was added, the organic layer separated, and the aqueous
phase extracted with Et2O (4×10 mL). The combined extracts were
washed with brine, dried (Na2SO4) and the solvents evaporated in
vacuo. The crude product was purified by column chromatography
to give the desired alcohols.
89%) as a colourless solid after column chromatography. Rf = 0.24
(pentane/Et2O, 4:1). H NMR (300 MHz, CDCl3): δ = 8.21 (dd, J
1
= 8.5, 0.6 Hz, 1 H, 8Ј-H), 7.79 (d, J = 9.0 Hz, 1 H, 4Ј-H), 7.78 (d,
J = 8.1 Hz, 1 H, 5Ј-H), 7.53–7.61 (m, 1 H, 7Ј-H), 7.38–7.46 (m, 3
H, 6Ј-H, 2ЈЈ-H, 6ЈЈ-H), 7.23–7.35 (m, 4 H, 3Ј-H, 3ЈЈ-H, 4ЈЈ-H, 5ЈЈ-
H), 5.06 (dd, J = 7.3, 3.4 Hz, 1 H, 2-H), 4.44 (dd, J = 9.6, 3.4 Hz,
1 H, 1-Ha), 4.33 (dd, J = 9.6, 7.3 Hz, 1 H, 1-Hb), 2.99 (br. s, 1 H,
OH) ppm. 13C NMR (75.5 MHz, CDCl3): δ = 152.6 (C-2Ј), 133.0
(C-8Јa), 131.8 (C-2ЈЈ, C-6ЈЈ), 130.4 (C-4Јa), 129.1 (C-4ЈЈ), 128.7 (C-
4Ј), 128.3 (C-3ЈЈ, C-5ЈЈ), 128.1 (C-5Ј), 127.9 (C-7Ј), 126.3 (C-8Ј),
4680
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© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2006, 4676–4684

Pd-Catalysed Synthesis of Acenaphthylenes
FULL PAPER
124.9 (C-6Ј), 122.0 (C-1ЈЈ), 116.0 (C-3Ј), 110.6 (C-1Ј), 86.33 (C-3),
7.2 Hz, 1 H, 1-Hb), 3.05 (d, J = 5.0 Hz, OH), 2.28 (s, 3 H, Me)
85.55 (C-4), 74.21 (C-1), 62.02 (C-2) ppm. IR (KBr): ν = 3376 ppm. 13C NMR (75.6 MHz, CDCl3): δ = 152.6 (C-2Ј), 137.9 (C-
˜
(OH), 3053, 2929, 2873 (CH) cm–1. UV (CH3CN): λmax (lgε) = 3ЈЈ), 133.0 (C-8Јa), 132.4 (C-2ЈЈ), 130.4 (C-4Јa), 129.6 (C-6ЈЈ), 129.1
282.0 (3.790), 250 (4.371), 232 (4.882), 202 nm (4.623). MS (70 eV, (C-4Ј), 128.9, 128.05 (C-4ЈЈ, C-5ЈЈ), 128.1 (C-5Ј), 127.8 (C-7Ј), 126.3
EI): m/z (%) = 287.2 (100) [C20H15O2]+, 131.1 (64) [C9H7O]+, 222.0
(95) [C10H6BrO]+, 115.1 (100) [C9H7]+, 77.0 (62) [C6H5]+. HRMS
(EI): 366.0256. C20H15BrO2 [M]+ requires 366.0255. C20H15BrO2
(367.23): calcd. C 65.41, H 4.12; found C 62.54, H 3.94.
(C-8Ј), 124.9 (C-6Ј), 121.8 (C-1ЈЈ), 116.0 (C-3Ј), 110.6 (C-1Ј), 86.50
(C-3), 85.20 (C-4), 74.23 (C-1), 62.02 (C-2), 21.16 (C-Me) ppm. IR
(KBr): ν = 3384 (OH), 2923 (C–H), 2231 (C C ), 1271 (O–Ar)
˜
sp sp
cm–1. UV (CH3CN): λmax (lgε) = 334.0 (3.302), 322.5 (3.262), 294.5
(3.671), 282.0 (3.785), 251.0 (4.336), 231.5 nm (4.853). MS (70 eV,
EI): m/z (%) = 380.2 (2) [M]+, 301.3 (34) [M – Br]+, 222.1 (58)
[C10H6BrO]+, 115.1 (100) [C9H7]+, 91.1 (28) [C7H7]+. C21H17BrO2
(381.26): calcd. C 66.16, H 4.49; found C 65.92, H 4.28.
1-(1-Bromonaphth-2-yloxy)-4-(4-fluorophenyl)but-3-yn-2-ol
(4d):
Reaction of aldehyde 6 (250 mg, 0.943 mmol) and alkyne 7d
(227 mg, 1.89 mmol) according to general procedure II afforded
4d (236 mg, 0.613 mmol, 65%) as a colourless solid after column
chromatography. Rf
=
0.10 (pentane/Et2O, 4:1). 1H NMR
1-(1-Bromonaphth-2-yloxy)-4-(2-methylphenyl)but-3-yn-2-ol
(4g):
(600 MHz, CDCl3): δ = 8.20 (dd, J = 8.6, 0.7 Hz, 1 H, 8Ј-H), 7.78
Reaction of aldehyde 6 (200 mg, 0.754 mmol) and alkyne 7g
(t, J = 8.9 Hz, 2 H, 4Ј-H, 5Ј-H), 7.55–7.59 (m, 1 H, 7Ј-H), 7.37– (175.3 mg, 1.51 mmol) according to general procedure II afforded
7.44 (m, 3 H, 6Ј-H, 2ЈЈ-H, 6ЈЈ-H), 7.28 (d, J = 9.1 Hz, 1 H, 3Ј-H) 4g (218.5 mg, 76%) as a colourless solid after column chromatog-
ppm. 6.94–6.99 (m, 2 H, 3ЈЈ-H, 5ЈЈ-H), 5.03 (ddd, J = 7.2, 5.2,
3.4 Hz, 1 H, 2-H), 4.43 (dd, J = 9.6, 3.4 Hz, 1 H, 1-Ha), 4.32 (dd,
J = 9.6, 7.2 Hz, 1 H, 1-Hb), 2.99 (d, J = 5.2 Hz, 1 H, OH) ppm.
13C NMR (75.5 MHz, CDCl3): δ = 164.4, 161.0 (C-4ЈЈ*), 152.6 (C-
2Ј), 133.8, 133.7 (C-2ЈЈ*, C-6ЈЈ*), 133.0 (C-8Јa), 130.4 (C-4Јa), 129.1
(C-4Ј), 128.1 (C-5Ј), 127.9 (C-7Ј), 126.3 (C-8Ј), 125.0 (C-6Ј), 118.2,
raphy. Rf = 0.26 (pentane/Et2O, 3:1). 1H NMR (300 MHz, CDCl3):
δ = 8.21 (d, J = 8.6 Hz, 1 H, 8Ј-H), 7.79 (d, J = 9.0 Hz, 1 H, 4Ј-
H), 7.78 (mc, 1 H, 5Ј-H), 7.57 (ddd, J = 8.6, 6.9, 1.3 Hz, 1 H, 7Ј-
H), 7.38–7.45 (m, 2 H, 6Ј-H, 6ЈЈ-H), 7.28 (d, J = 9.0 Hz, 1 H, 3Ј-
H), 7.07–7.25 (m, 3 H, 5ЈЈ-H, 4ЈЈ-H, 3ЈЈ-H), 5.10 (ddd, J = 7.1, 5.2,
3.4 Hz, 1 H, 2-H), 4.44 (dd, J = 9.6, 3.4 Hz, 1 H, 1-Ha), 4.35 (dd,
118.1 (C-1ЈЈ*), 116.0 (C-3Ј), 115.7, 115.4 (C-3ЈЈ*, C-5ЈЈ*), 110.6 (C- J = 9.6, 7.1 Hz, 1 H, 1-Hb), 3.01 (d, J = 5.2 Hz, 1 H, OH), 2.42 (s,
1Ј), 85.39 (C-3), 85.28 (C-4), 74.17 (C-1), 61.97 (C-2) ppm. IR
3 H, Me) ppm. 13C NMR (75.5 MHz, CDCl3): δ = 152.6 (C-2Ј),
140.4 (C-2ЈЈ), 133.0 (C-8Јa), 132.2 (C-6ЈЈ), 130.4 (C-4Јa), 129.4 (C-
3ЈЈ), 129.1 (C-4Ј), 128.7 (C-4ЈЈ), 128.1 (C-5Ј), 127.8 (C-7Ј), 126.3
(C-8Ј), 125.5 (C-5ЈЈ), 124.9 (C-6Ј), 121.8 (C-1ЈЈ), 116.0 (C-3Ј), 110.5
(C-1Ј), 89.47 (C-3), 85.16 (C-4), 74.27 (C-1), 62.10 (C-2), 20.65 (C-
(KBr): ν = 3363 (OH), 3048, 2873 (C–H), 1149 (O–Ar) cm–1. UV
˜
(CH3CN): λmax (lgε) = 334.0 (3.332), 322.5 (3.294), 294.5 (3.698),
283.0 (3.807), 273.5 (3.734), 231.0 nm (4.882). MS (70 eV, EI): m/z
(%) = 384.2 (16) [M]+, 305.2 (100) [M – Br]+, 222.1 (95)
[C6H6BrO]+, 149.1 (42) [C9H6FO]+, 126.1 (50) [C10H6]+.
Me) ppm. IR (KBr): ν = 3554 (OH), 3051, 2926 (C–H), 1451
˜
C20H14BrFO2 (385.23): calcd. C 62.36, H 3.66; found C 62.11, H (CH2), 1267 (Ar–O), 761 (Ar–Me) cm–1. UV (CH3CN): λmax (lgε)
3.48.
= 334.0 (3.338), 322.5 (3.296), 294.5 (3.686), 282.0 (3.814), 273.0
(3.729), 251.0 (4.324), 231.0 nm (4.872). MS (70 eV, EI): m/z (%) =
382.0 (3) [M]+, 301.1 (58) [M – Br]+, 283.1 (14) [M – Br-OH]+,
221.9 (100) [C10H6BrO]+, 209.0 (53) [C14H9O2]+, 126.0 (42)
[C10H8]+, 115.0 (80) [C9H7]+, 91.0 (34) [C7H7]+. C21H17BrO2
(381.26): calcd. C 66.16, H 4.49; found C 66.32, H 4.29.
1-(1-Bromonaphth-2-yloxy)-4-(2-trifluoromethylphenyl)but-3-yn-2-ol
(4e): Reaction of aldehyde 6 (250 mg, 0.943 mmol) and alkyne 7e
(320.8 mg, 1.89 mmol) according to general procedure II afforded
4e (356.2 mg, 87%) as colourless solid after column chromatog-
raphy. Rf = 0.21 (pentane/Et2O, 3:1). 1H NMR (300 MHz, CDCl3):
δ = 8.20 (d, J = 8.6 Hz, 1 H, 8Ј-H), 7.78 (d, J = 9.0 Hz, 1 H, 4Ј-
H), 7.77 (dt, J = 8.1, 0.6 Hz, 1 H, 5Ј-H), 7.53–7.66 (m, 3 H, 7Ј-H,
1-(1-Bromonaphth-2-yloxy)oct-3-yn-2-ol (4h): Reaction of aldehyde
6 (250 mg, 0.943 mmol) and alkyne 7h (93.0 mg, 1.13 mmol) ac-
4ЈЈ-H, 6ЈЈ-H), 7.33–7.48 (m, 3 H, 6Ј-H, 3ЈЈ-H, 5ЈЈ-H), 7.27 (d, J = cording to general procedure II afforded 4h (286 mg, 87%) as a
9.0 Hz, 1 H, 3Ј-H), 5.10 (mc, 1 H, 2-H), 4.44 (dd, J = 9.7, 3.4 Hz, colourless oil after column chromatography. Rf = 0.18 (pentane/
1 H, 1-Ha), 4.34 (dd, J = 9.7, 7.3 Hz, 1 H, 1-Hb), 3.07 (br. s, 1 H,
Et2O, 5:1). 1H NMR (300 MHz, CDCl3): δ = 8.20 (mc, 1 H, 8Ј-H),
OH) ppm. 13C NMR (75.5 MHz, CDCl3): δ = 152.6 (C-2Ј), 134.2 7.78 (d, J = 8.9 Hz, 1 H, 4Ј-H), 7.74–7.79 (m, 1 H, 5Ј-H), 7.56
(C-4ЈЈ), 133.0 (C-2ЈЈ), 131.6 (C-8Јa), 131.4 (C-5ЈЈ), 131.3 (C-4Јa), (ddd, J = 8.5, 7.0, 1.4 Hz, 1 H, 7Ј-H), 7.41 (ddd, J = 8.0, 7.0,
129.2 (C-4Ј), 128.5 (C-3ЈЈ), 128.1 (C-5Ј), 127.9 (C-7Ј), 126.3 (C-8Ј), 1.2 Hz, 1 H, 6Ј-H), 7.23 (d, J = 8.9 Hz, 1 H, 3Ј-H), 4.83 (mc, 1 H,
125.8 (C-6ЈЈ), 125.2 (C–CF3), 124.9 (C-6Ј), 121.6 (C-1ЈЈ), 116.1 (C- 2-H), 4.32 (dd, J = 9.8, 3.4 Hz, 1 H, 1-Ha), 4.18 (dd, J = 9.8,
3Ј), 110.6 (C-1Ј), 91.23 (C-3), 82.18 (C-4), 73.94 (C-1), 62.03 (C-2)
7.7 Hz, 1 H, 1-Hb), 2.81 (d, J = 4.4 Hz, 1 H, OH), 2.22 (td, J =
ppm. IR (KBr): ν = 3330 (OH), 2943, 2874 (C–H), 1451 (CH ) 7.0, 2.0 Hz, 2 H, 5-H), 1.31–1.53 (m, 4 H, 6-H, 7-H), 0.88 (t, J =
˜
2
cm–1. UV (CH3CN): λmax (lgε) = 334.0 (3.316), 322.0 (3.278), 285.5
7.2 Hz, 3 H, 8-H) ppm. 13C NMR (75.5 MHz, CDCl3): δ = 152.6
(C-2Ј), 133.0 (C-8Јa), 130.3 (C-4Јa), 129.0 (C-4Ј), 128.0 (C-5Ј),
(3.905), 280.0 (3.917), 231.0 nm (4.861). MS (70 eV, EI): m/z (%) =
434.1 (32) [M]+, 355.2 (60) [M – Br]+, 224.0 (100) [C10H6BrO]+, 127.8 (C-7Ј), 126.3 (C-8Ј), 124.8 (C-6Ј), 116.0 (C-3Ј), 110.4 (C-1Ј),
156.1 (17) [C11H8O]+. C21H14BrF3O2 (435.23): calcd. C 57.95, H 87.44 (C-4), 76.58 (C-3), 74.54 (C-1), 61.65 (C-2), 30.43 (C-6), 21.88
3.24; found C 57.71, H 3.01.
(C-7), 18.37 (C-5), 13.54 (C-8) ppm. IR (KBr): ν = 3396 (OH),
˜
2932, 2871 (C–H), 2238 (CspCsp), 1464 (CH2) cm–1. UV (CH3CN):
λmax (lgε) = 334.0 (3.352), 322.5 (3.310), 294.5 (3.713), 282.5
(3.790), 232.0 nm (4.875). MS (70 eV, EI): m/z (%) = 346.1 (18)
[M]+, 267.2 (4) [M – Br]+, 224.0 (100) [C16H16O]+, 126.1 (20)
[C10H6]+. C18H19BrO2 (346.26): calcd. 346.0568; found 346.0568.
1-(1-Bromonaphth-2-yloxy)-4-(3-methylphenyl)but-3-yn-2-ol
(4f):
Reaction of aldehyde 6 (200 mg, 0.754 mmol) and alkyne 7f
(175 mg, 1.51 mmol) according to general procedure II afforded 4f
(260 mg, 90%) as a colourless solid after column chromatography.
Rf = 0.16 (pentane/Et2O, 4:1). 1H NMR (300 MHz, CDCl3): δ =
8.21 (d, J = 8.4 Hz, 1 H, 8Ј-H), 7.75–7.81 (m, 2 H, 4Ј-H, 5Ј-H),
1-(1-Bromonaphth-2-yloxy)-5,5-dimethylhex-3-yn-2-ol (4i): Reaction
7.57 (ddd, J = 8.4, 7.0, 1.4 Hz, 1 H, 7Ј-H), 7.42 (ddd, J = 8.3, 7.0, of aldehyde 6 (200 mg, 0.754 mmol) and alkyne 7i (123.9 mg,
1.3 Hz, 1 H, 6Ј-H), 7.27 (d, J = 8.9 Hz, 1 H, 3Ј-H), 7.08–7.25 (m, 1.51 mmol) according to general procedure II afforded 4i (229 mg,
4 H, 2ЈЈ-H, 4ЈЈ-H, 5ЈЈ-H, 6ЈЈ-H), 5.06 (ddd, J = 7.2, 5.0, 3.4 Hz, 1
88%) as a colourless oil after column chromatography. Rf = 0.16
H, 2-H), 4.43 (dd, J = 9.7, 3.4 Hz, 1 H, 1-Ha), 4.33 (dd, J = 9.7, (pentane/Et2O, 6:1). 1H NMR (600 MHz, CDCl3): δ = 8.20 (d, J
Eur. J. Org. Chem. 2006, 4676–4684
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
4681

L. F. Tietze, F. Lotz
FULL PAPER
= 8.6 Hz, 1 H, 8Ј-H), 7.76–7.81 (m, 2 H, 4Ј-H, 5Ј-H), 7.56 (ddd, J (C-7a), 126.4 (C-6, C-7), 125.9 (C-5), 124.2 (C-4a), 123.9, 123.6,
= 8.6, 7.0, 1.2 Hz, 1 H, 7Ј-H), 7.42 (ddd, J = 8.0, 7.0, 1.2 Hz, 1 H, (C-4Ј, C-6Ј), 121.1 (C-9b), 119.4 (C-3Ј), 118.5 (C-2ЈЈ, C-6ЈЈ), 118.0
6Ј-H), 7.27 (d, J = 9.0 Hz, 1 H, 3Ј-H), 4.81 (dd, J = 7.8, 3.2 Hz, 1 (C-9), 75.83 (C-2), 65.27 (C-3) ppm. IR (KBr): ν = 3051 (C–H),
˜
H, 2-H), 4.31 (dd, J = 9.6, 3.2 Hz, 1 H, 1-Ha), 4.17 (dd, J = 9.6, 1666 (C=C), 1481 (CH2), 1230 (Ar–O) cm–1. UV (CH3CN): λmax
7.8 Hz, 1 H, 1-Hb), 2.73 (br. s, 1 H, OH), 1.19 (s, 9 H, tBu) ppm.
(lgε) = 362.5 (3.744), 378.0 (3.820), 323.0 (3.753), 309.5 nm (3.656).
13C NMR (75.5 MHz, CDCl3): δ = 152.6 (C-2Ј), 132.9 (C-8Јa),
MS (70 eV, EI): m/z (%) = 378.3 (100) [M]+, 361.3 (78) [M –
130.3 (C-4Јa), 129.0 (C-4Ј), 128.0 (C-5Ј), 127.8 (C-7Ј), 126.2 (C-8Ј), OH]+, 285.2 (36) [M – C6H5O]+, 255.2 (43) [M – C6H3O3]+, 226.2
124.8 (C-6Ј), 116.0 (C-3Ј), 110.4 (C-1Ј), 95.39 (C-4), 75.05 (C-3),
74.55 (C-1), 61.58 (C-2), 30.77 (3×C-Me), 27.30 (C-5) ppm. IR C20H13O3]+. C26H18O3 (378.42): calcd. C 82.52, H 4.79; found
(KBr): ν = 3422 (OH), 3067 (C–H), 2236 (C C ), 1452 (CH ), C 80.78, H 4.73.
(50) [M – C8H8O3]+, 181.2 (14) [M – C13H8O2]+, 77.1 (16) [M –
˜
sp sp
2
1274 (O–Ar) cm–1. UV (CH3CN): λmax (lgε) = 334.0 (3.327), 322.5
(3.293), 294.5 (3.691), 282.5 (3.773), 273.5 (3.663), 231.5 nm
(4.865). MS (70 eV, EI): m/z (%) = 346.2 (24) [M]+, 222.0 (100)
[C10H6BrO]+, 193.1 (5) [C14H9O]+, 126.1 (9) [C8H13O]+.
C18H19BrO2 (347.25): calcd. C 62.26, H 5.52; found C 61.93, H
5.49.
Resolution: HPLC: Flow: 0.8 mL/min, eluent: n-hexane/iPrOH,
95:5, tR,I = 47.88 min, tR,II = 58.51 min.
4-(4-Methoxyphenyl)-2,3-dihydro-1-oxacyclopenta[def]phenanthren-
3-ol (5b): Reaction of 4b (90.0 mg, 0.227 mmol) according to gene-
ral procedure III at 125 °C for 3 h yielded 5b (68.1 mg, 0.215 mmol,
1
95%) as an orange foam. Rf = 0.22 (pentane/Et2O, 2:1). H NMR
1-(1-Bromonaphth-2-yloxy)-4-trimethylsilylbut-3-yn-2-ol (4k): Reac-
tion of aldehyde 6 (250 mg, 0.943 mmol) and alkyne 7k (185.2 mg,
1.89 mmol) according to general procedure II afforded 4k
(315.9 mg, 92%) as a colourless oil after column chromatography.
Rf = 0.21 (pentane/Et2O, 6:1). 1H NMR (600 MHz, CDCl3): δ =
8.20 (d, J = 8.6 Hz, 1 H, 8Ј-H), 7.76–7.80 (m, 2 H, 4Ј-H, 5Ј-H),
7.57 (ddd, J = 8.6, 7.0, 1.2, 1 H, 7Ј-H), 7.42 (ddd, J = 8.0, 7.0,
1.2 Hz, 1 H, 6Ј-H), 7.27 (d, J = 9.0 Hz, 1 H, 3Ј-H), 4.82 (dd, J =
7.6, 3.5 Hz, 1 H, 2-H), 4.35 (dd, J = 9.7, 3.5 Hz, 1 H, 1-Ha), 4.22
(dd, J = 9.7, 7.6 Hz, 1 H, 1-Hb), 2.78 (br. s, 1 H, OH), 0.15 (s, 9
H, SiMe3) ppm. 13C NMR (75.5 MHz, CDCl3): δ = 152.6 (C-2Ј),
133.0 (C-8Јa), 130.4 (C-4Јa), 129.1 (C-4Ј), 128.1 (C-5Ј), 127.9 (C-
7Ј), 126.3 (C-8Ј), 124.9 (C-6Ј), 116.1 (C-3Ј), 110.6 (C-1Ј), 101.9 (C-
3), 91.60 (C-4), 74.19 (C-1), 61.94 (C-2), –0.20 (SiMe3) ppm. IR
(600 MHz, CDCl3): δ = 7.99 (d, J = 7.0 Hz, 1 H, 5-H*), 7.79–7.84
(m, 3 H, 3Ј-H, 5Ј-H, 7-H*), 7.73 (d, J = 8.8 Hz, 1 H, 8-H), 7.53
(dd, J = 8.0, 7.0 Hz, 1 H, 6-H), 7.10 (d, J = 8.8 Hz, 1 H, 9-H), 7.04
(mc, 2 H, 2Ј-H, 6Ј-H), 5.07 (mc, 1 H, 3-H), 4.72 (dd, J = 12.0,
9.6 Hz, 1 H, 2-Ha), 4.39 (dd, J = 12.0, 9.8 Hz, 1 H, 2-Hb), 3.86 (s,
3 H, OMe), 2.24 (br. s, 1 H, OH) ppm. 13C NMR (50.3 MHz,
CDCl3): δ = 159.1 (C-4Ј), 152.9 (C-9a), 138.7 (C-3a), 132.6 (C-4),
130.1 (C-7), 129.9 (C-2Ј, C-6Ј), 127.9 (C-1Ј), 127.6 (C-9c), 126.7
(C-8), 126.6, 126.5 (C-6, C-5), 126.5 (C-4a), 124.5 (C-7a), 121.3 (C-
9b), 118.0 (C-9), 114.5 (C-3Ј, C-5Ј), 76.93 (C-2), 64.62 (C-3), 55.34
(C–OMe) ppm. IR (KBr): ν = 3418 (OH), 2908 (C–H), 1665
˜
(C=C), 1441 (CH2) cm–1. UV (CH3CN): λmax (lgε) = 419.0 (3.527),
381.5 (3.936), 364.5 (3.833), 322.5 (3.906), 307.5 (3.857), 271.5
(4.168), 232.5 nm (4.422). MS (70 eV, EI): m/z (%) = 316.2 (100),
[M]+, 299.2 (47) [M – OH]+, 283.2 (22) [C20H11O2]+, 226.1 (17)
[C18H9]+, 149.1 (5) [C12H5]+. C21H16O3 (316.36): calcd. 316.1099;
found 316.1099.
(KBr): ν = 3532 (OH), 3067 (C–H), 2177 (C C ), 1452 (CH ),
˜
sp sp
2
1273 (O–Ar) cm–1. UV (CH3CN): λmax (lgε) = 334.0 (3.285), 322.0
(3.247), 294.5 (3.658), 282.5 (3.737), 273.5 (3.628), 231.5 nm
(4.829). MS (70 eV, EI): m/z (%) = 364.2 (22) [M]+, 267.2 (3) [M –
Br-OH]+, 222.1 (100), [C10H6BrO]+, 193.1 (30) [C14H9O]+, 73.1 (63)
[SiMe3]+. C17H19BrO2Si (363.32): calcd. C 56.20, H 5.27; found
C 55.98, H 4.98.
Resolution: HPLC: Flow: 0.8 mL/min, eluent: n-hexane/iPrOH,
95:5, tR,I = 49.21 min, tR,II = 84.84 min.
4-Phenyl-2,3-dihydro-1-oxacyclopenta[def]phenanthren-3-ol (5c): Re-
action of 4c (100 mg, 0.272 mmol) according to general procedure
III at 130 °C for 3 h yielded 5c (59.2 mg, 76%) as an orange foam.
Rf = 0.24 (pentane/Et2O, 4:1). 1H NMR (600 MHz, CDCl3): δ =
8.02 (d, J = 7.1 Hz, 1 H, 7-H*), 7.86–7.89 (m, 2 H, 2Ј-H, 6Ј-H),
7.81 (d, J = 8.0 Hz, 1 H, 5-H*), 7.76 (d, J = 8.8 Hz, 1 H, 8-H),
7.54 (dd, J = 8.0, 7.1 Hz, 1 H, 6-H), 7.50 (mc, 2 H, 3Ј-H, 5Ј-H),
7.37 (mc, 1 H, 4Ј-H), 7.11 (d, J = 8.8 Hz, 1 H, 9-H), 5.09 (mc, 1 H,
3-H), 4.72 (dd, J = 12.0, 2.3 Hz, 1 H, 2-Ha), 4.39 (dd, J = 12.0,
2.3 Hz, 1 H, 2-Hb), 2.26 (br. s, 1 H, OH) ppm. 13C NMR
(50.3 MHz, CDCl3): δ = 153.3 (C-9a), 138.5 (C-1Ј), 135.3 (C-3a),
132.8 (C-4), 130.6 (C-7), 129.0 (C-2Ј, C-6Ј), 128.7 (C-3Ј, C-5Ј),
127.8 (C-9c, C-4a), 127.4 (C-8), 126.8, 126.7, 126.6 (C-4Ј, C-6, C-
5), 124.5 (C-7a), 121.1 (C-9b), 118.0 (C-9), 76.93 (C-2), 64.60 (C-
General Procedure III
Palladium-Catalysed Domino Cyclisation of 4: palladacycle 14
(0.1 equiv.) was added to a stirred mixture of 4.0 equiv. lithium ace-
tate, 3.0 equiv. tetrabutylammonium acetate, 1.0 equiv. of 4 in
(CH3CN/DMF/H2O, 5:5:1, 28 mL/mol) at 60 °C and stirring was
continued with reflux at 120–140 °C. For quenching the reaction,
water was added (1 mL/mmol) and the mixture was extracted with
Et2O. The organic layers were washed with brine and dried
(MgSO4). After evaporation of the solvent the residue was purified
by column chromatography.
4-(2-Phenoxyphenyl)-2,3-dihydro-1-oxacyclopenta[def]phenanthren-
3-ol (5a): Reaction of 4a (90 mg, 0.196 mmol) according to general
procedure III at 120 °C for 2 h yielded 5a (70 mg, 94%) as a yellow
3) ppm. IR (KBr): ν = 3386 (OH), 3050, 2908 (C–H), 1664 (C=C),
˜
1
1441 (CH2) cm–1. UV (CH3CN): λmax (lgε) = 364.5 (3.901), 380.0
(4.001), 323.5 (3.920), 309.0 (3.810), 245.5 nm (4.345). MS (70 eV,
EI): m/z (%) = 286.1 (100) [M]+, 269.1 (68) [M – OH]+, 239.1 (34)
[M – CH3O2]+, 226.1 (32) [M – C2H4O2]+. C20H14O2 (286.32):
calcd. 286.0994; found 286.0994.
foam. Rf = 0.27 (pentane/ethyl acetate, 7:1). H NMR (600 MHz,
CDCl3): δ = 7.86 (d, J = 7.1 Hz, 1 H, 5-H*), 7.80 (d, J = 7.9 Hz,
1 H, 7-H*), 7.78 (d, J = 8.8 Hz, 1 H, 8-H), 7.75 (dd, J = 7.5, 1.7 Hz,
1 H, 4ЈЈ-H), 7.52 (dd, J = 7.9, 7.1 Hz, 1 H, 6-H), 7.34 (mc, 1 H,
5Ј-H), 7.29 (mc, 1 H, 4Ј-H), 7.24 (mc, 2 H, 3ЈЈ-H, 5ЈЈ-H), 7.12 (d,
J = 8.8 Hz, 1 H, 9-H), 7.05 (dd, J = 8.0, 1.1 Hz, 1 H, 6Ј-H*), 7.02
(dt, J = 7.5, 0.9 Hz, 1 H, 3Ј-H*), 6.95 (mc, 2 H, 2ЈЈ-H, 6ЈЈ-H), 5.26
(mc, 1 H, 3-H), 4.62 (dd, J = 11.7, 4.6 Hz, 1 H, 2-Ha), 4.44 (dd, J
= 11.7, 3.0 Hz, 1 H, 2-Hb), 3.05 (d, J = 4.0 Hz, 1 H, OH) ppm.
13C NMR (50.3 MHz, CDCl3): δ = 156.6 (C-2), 154.2, 153.5 (C-
Resolution: HPLC: Flow: 0.8 mL/min, eluent: n-hexane/iPrOH,
95:5, tR,I = 31.45 min, tR,II = 46.16 min.
4-(4-Fluorophenyl)-2,3-dihydro-1-oxacyclopenta[def]phenanthren-3-
ol (5d): Reaction of 4d (70 mg, 0.182 mmol) according to general
1ЈЈ, C-9a), 139.5 (C-1Ј), 132.2 (C-4ЈЈ), 131.0 (C-3a), 130.5 (C-8), procedure III at 130 °C for 4.5 h yielded 5d (41.8 mg, 76%) as yel-
129.8 (C-3ЈЈ, C-5ЈЈ), 128.8 (C-5Ј*), 127.6 (C-4), 127.0 (C-9c), 126.7
low foam. Rf = 0.23 (pentane/Et2O, 4:1). 1H NMR (300 MHz,
4682
www.eurjoc.org
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2006, 4676–4684

Pd-Catalysed Synthesis of Acenaphthylenes
FULL PAPER
CDCl3): δ = 7.96 (d, J = 7.0 Hz, 1 H, 5-H), 7.80–7.87 (m, 2 H, 2Ј- Resolution: HPLC: Flow: 0.8 mL/min, eluent: n-hexane/iPrOH,
H, 6Ј-H), 7.81 (d, J = 8.0 Hz, 1 H, 7-H), 7.75 (d, J = 8.8 Hz, 1 H, 95:5, tR,I = 33.23 min, tR,II = 46.40 min.
8-H), 7.53 (dd, J = 8.0, 7.0 Hz, 1 H, 6-H), 7.19 (mc, 2 H, 3Ј-H, 5Ј-
4-(2-Methylphenyl)-2,3-dihydro-1-oxacyclopenta[def]phenanthrene-
H), 7.10 (d, J = 8.0 Hz, 1 H, 9-H), 5.03 (mc, 1 H, 3-H), 4.71 (dd,
3-ol (5g): Reaction of 4g (70 mg, 0.184 mmol) according to general
J = 12.1, 2.4 Hz, 1 H, 2-Ha), 4.38 (dd, J = 12.1, 2.4 Hz, 1 H, 2-
procedure III at 140 °C for 2.5 h yielded 5g (53.9 mg, 98%) as a
Hb), 2.18 (br. s, 1 H, OH) ppm. 13C NMR (50.3 MHz, CDCl3): δ
1
yellow foam. Rf = 0.34 (pentane/Et2O, 3:1). H NMR (300 MHz,
= 163.9 (C-4Ј), 160.6 (C-9a), 153.3 (C-3a), 138.3 (C-4), 131.8 (C-
CDCl3): δ = 7.75–7.82 (m, 2 H, 5-H, 8-H), 7.61 (mc, 1 H, 7-H),
1Ј), 131.4 (C-9c), 130.6 (C-7), 130.3 (d, J = 8.1 Hz, 2 C, C-2Ј*, C-
7.44–7.51 (m, 2 H, 3Ј-H, 6-H), 7.22–7.37 (m, 3 H, 4Ј-H, 5Ј-H, 6Ј-
6Ј*), 127.5 (C-4a), 126.9 (C-8), 126.6, 126.5 (C-6, C-5), 124.5 (C-
H), 7.12 (d, J = 8.8 Hz, 1 H, 9-H), 5.02 (mc, 1 H, 3-H), 4.52 (dd,
7a), 121.0 (C-9b), 118.0 (C-9), 116.0 (d, J = 21.3 Hz, 2 C, C-3Ј, C-
J = 11.5, 4.5 Hz, 1 H, 2-Ha), 4.42 (dd, J = 11.7, 3.1 Hz, 1 H, 2-
5Ј), 76.95 (C-2), 64.49 (C-3) ppm. IR (KBr): ν = 3356 (OH), 2917
˜
Hb), 2.40 (s, 3 H, Me), 2.16 (mc, 1 H, OH) ppm. 13C NMR
(75.5 MHz, CDCl3): δ = 153.2 (C-9a), 139.9 (C-1Ј, C-2Ј), 134.2 (C-
3a), 132.7 (C-4), 130.5 (C-3Ј, C-4Ј), 130.4 (C-8), 129.8 (C-9c), 127.8
(C-5Ј), 127.4 (C-4a), 126.5 (C-6), 126.4 (C-5), 126.0 (C-7), 125.7
(C-6Ј), 124.3 (C-7a), 121.0 (C-9b), 117.9 (C-9), 76.31 (C-2), 65.32
(C–H), 1665 (C=C), 1441 (CH2) cm–1. UV (CH3CN): λmax (lgε) =
380.0 (3.990), 364.5 (3.889), 323.0 (3.919), 309.0 (3.805), 245.0 nm
(4.353). MS (70 eV, EI): m/z (%) = 304.2 (100) [M]+, 287.2 (68),
[M – OH]+, 262.2 (30) [C18H11FO]+, 257.1 (36) [C19H10F]+, 244.2
(40) [C18H9F]+, 122.1 (35) [C8H7F]+. C20H13FO2 (304.31): calcd.
C 78.94, H 4.31; found C 78.82, H 4.43.
(C-3), 20.79 (C-Me) ppm. IR (KBr): ν = 3387 (OH), 2920 (C–H),
˜
1667 (C=C), 1442 (CH2), 1210 (Ar–O) cm–1. UV (CH3CN): λmax
(lgε) = 374.0 (3.958), 359.5 (3.891), 320.5 (3.920), 307.0 (3.793),
240.5 nm (4.412). MS (70 eV, EI): m/z (%) = 300.1 (92) [M]+, 283.1
(100) [M – OH]+, 239.1 (94) [C19H11]+, 226.1 (55) [C18H10]+, 126.0
(37) [C10H6]+, 91.0 (8) [C7H7]+. [C21H16O2 + H]+ (301.36): calcd.
301.1223; found 301.1223.
Resolution: HPLC: Flow: 0.8 mL/min, eluent: n-hexane/iPrOH,
95:5, tR,I = 36.65 min, tR,II = 62.08 min.
4-(2-Trifluoromethylphenyl)-2,3-dihydro-1-oxacyclopenta[def]phen-
anthren-3-ol (5e): Reaction of 4e (90 mg, 0.207 mmol) according to
general procedure III at 140 °C for 4.5 h yielded 5e (65.8 mg, 69%)
as a yellow foam. Rf = 0.33 (pentane/Et2O, 2:1). 1H NMR
(300 MHz, CDCl3): δ = 7.78–7.86 (m, 2 H, 7-H*, 5-H*), 7.81 (d, J
= 8.9 Hz, 1 H, 8-H), 7.42–7.65 (m, 5 H, 6-H*, 3Ј-H*, 4Ј-H*, 5Ј-
H*, 6Ј-H*), 7.14 (d, J = 8.9 Hz, 1 H, 9-H), 5.01–5.07 (m, 1 H, 3-
H), 4.57 (dd, J = 11.9, 4.0 Hz, 1 H, 2-Ha), 4.45 (dd, J = 11.9,
2.8 Hz, 1 H, 2-Hb), 1.87 (br. s, 1 H, OH) ppm. 13C NMR
(75.5 MHz, CDCl3): δ = 153.7 (C-9a), 140.7 (C-3a), 133.7 (C-1Ј*),
132.7 (C-5Ј*), 131.4 (C-4Ј*), 131.2 (C-4*), 130.9 (C-8*), 129.3 (C-
9c*), 128.2 (C-6*), 127.9 (C-3Ј*), 127.0 (C-2Ј*), 126.6 (C-7*), 126.4
(C-6Ј*), 126.0 (C-4a*), 125.4 (C-5*), 124.2 (C–CF3*), 122.3 (C-
7a*), 120.4 (C-9b*), 117.9 (C-9), 76.42 (C-2), 64.73 (C-3) ppm. IR
Resolution: HPLC: Flow: 0.8 mL/min, eluent: n-hexane/iPrOH,
95:5, tR,I = 26.88 min, tR,II = 29.63 min.
4-Butyl-2,3-dihydro-1-oxacyclopenta[def]phenanthren-3-ol (5h): Re-
action of 4h (90 mg, 0.259 mmol) according to general procedure
III at 140 °C for 22 h yielded 5h (25.2 mg, 37%) as a yellow oil. Rf
= 0.18 (pentane/Et2O, 5:1). 1H NMR (300 MHz, CDCl3): δ = 7.75,
(d, J = 6.9 Hz, 1 H, 7-H), 7.74 (d, J = 8.0 Hz, 1 H, 5-H), 7.66 (d,
J = 8.9 Hz, 1 H, 8-H), 7.47 (dd, J = 8.0, 6.9 Hz, 1 H, 6-H), 7.05
(d, J = 8.9 Hz, 1 H, 9-H), 5.07 (mc, 1 H, 3-H), 4.56 (dd, J = 11.9,
3.5 Hz, 1 H, 2-Ha), 4.33 (dd, J = 11.9, 2.9 Hz, 1 H, 2-Hb), 2.88 (t,
J = 7.7 Hz, 2 H, 1Ј-H), 1.99 (mc, 1 H, OH), 1.79 (mc, 2 H, 2Ј-H),
1.47 (mc, 2 H, 3Ј-H), 0.97 (t, J = 7.3 Hz, 3 H, 4Ј-H) ppm. 13C
NMR (75.5 MHz, CDCl3): δ = 151.9 (C-4), 140.1 (C-9a), 134.8 (C-
3a), 129.4 (C-8), 127.7, 127.5 (C-9c, C-4a), 126.3 (C-5), 126.2 (C-
6), 124.5 (C-7), 124.1 (C-7a), 121.0 (C-9b), 117.9 (C-9), 76.42 (C-
2), 64.84 (C-3), 32.79 (C-2Ј), 26.58 (C-1Ј), 22.91 (C-3Ј), 13.98 (C-
(KBr): ν = 3384 (OH), 2917 (C–H), 1668 (C=C), 1442 (CH ), 1231
˜
2
(Ar–O) cm–1. UV (CH3CN): λmax (lg ε) = 371.5 (3.964), 357.5
(3.905), 320.5 (3.962), 306.5 (3.841), 239.0 nm (4.376). MS (70 eV,
EI): m/z (%) = 354.3 (35) [M]+, 337.3 (34) [M – OH]+, 104.1 (86)
[C8H8]+, 77.1 (30) [C6H5]+, 66.0 [C4H2O]+. C21H13F3O2 (354.33):
calcd. 354.0868; found 354.0868.
4Ј) ppm. IR (KBr): ν = 3339 (OH), 2928, 2857 (C–H) cm–1. UV
˜
(CH3CN): λmax (lgε) = 369.0 (3.820), 353.0 (3.745), 316.5 (3.845),
302.5 (3.717), 232.0 nm (4.348). MS (70 eV, EI): m/z (%) = 266.3
(100) [M]+, 249.3 (18) [M – OH]+, 223.2 (95) [M – OH-C2H5]+,
195.2 (82) [M – OH-C4H9]+, 165.2 (69) [C12H5O]+. C18H18O2
(266.34): calcd. 266.1307; found 266.1307.
Resolution: HPLC: Flow: 0.8 mL/min, eluent: n-hexane/iPrOH,
95:5, tR,I = 28.39 min, tR,II = 29.97 min.
4-(3-Methylphenyl)-2,3-dihydro-1-oxacyclopenta[def]phenanthren-3-
ol (5f): Reaction of 4f (90 mg, 0.236 mmol) according to general
procedure III at 130 °C for 4.5 h yielded 5f (52.2 mg, 74%) as a
Resolution: HPLC: Flow: 0.8 mL/min, eluent: n-hexane/iPrOH,
95:5, tR,I = 31.71 min, tR,II = 38.60 min.
1
yellow foam. Rf = 0.19 (pentane/Et2O, 4:1). H NMR (300 MHz,
CDCl3): δ = 8.00 (d, J = 7.1 Hz, 1 H, 5-H), 7.79 (d, J = 8.0 Hz, 1
1-(2,2-Dimethylpropylidene)-2,3-dihydro-1H-benzo[f]chromen-2-ol
H, 7-H), 7.71 (d, J = 8.8 Hz, 1 H, 8-H), 7.63–7.69 (m, 2 H, 4Ј-H, (15): Reaction of 4i (90,0 mg, 0.26 mmol) according to general pro-
2Ј-H), 7.53 (dd, J = 8.0, 7.1 Hz, 1 H, 6-H), 7.39 (mc, 1 H, 5Ј-H), cedure III at 140 °C for 46 h yielded 15 (22.6 mg, 0.085 mmol,
1
7.16–7.21 (m, 1 H, 6Ј-H), 7.08 (d, J = 8.8 Hz, 1 H, 9-H), 5.05 (mc, 33%) as a colourless oil. Rf = 0.22 (pentane/Et2O, 3:1). H NMR
1 H, 3-H), 4.68 (dd, J = 12.1, 2.6 Hz, 1 H, 2-Ha), 4.33 (dd, J =
(300 MHz, CDCl3): δ = 8.29 (d, J = 8.6 Hz, 1 H, 10-H), 7.74 (dd,
12.1, 2.3 Hz, 1 H, 2-Hb), 2.42 (d, J = 7.9 Hz, 1 H, OH) ppm. 13C J = 8.0, 1.3 Hz, 1 H, 7-H), 7.62 (d, J = 8.9 Hz, 1 H, 6-H), 7.42
NMR (75.5 MHz, CDCl3): δ = 153.2 (C-9a), 138.5 (C-1Ј, C-3Ј), (ddd, J = 8.6, 6.9, 1.5 Hz, 1 H, 9-H), 7.31 (ddd, J = 8.0, 6.9, 1.2 Hz,
135.2 (C-3a), 132.8 (C-4), 130.3 (C-8), 129.2 (C-4Ј), 128.9 (C-5Ј), 1 H, 8-H), 7.03 (d, J = 8.9 Hz, 1 H, 5-H), 6.11 (s, 1 H, 1Ј-H), 5.28
128.1 (C-6Ј), 127.7 (C-9c), 127.6 (C-4a), 126.7 (C-5, C-7), 126.5 (C- (mc, 1 H, 2-H), 4.51 (dd, J = 11.8, 2.1 Hz, 1 H, 3-Ha), 4.28 (dd, J
6), 125.8 (C-2Ј), 124.4 (C-7a), 121.1 (C-9b), 117.9 (C-9), 76.83 (C-
= 11.8, 2.0 Hz, 1 H, 3-Hb), 2.00 (d, J = 5.5 Hz, 1 H, OH), 1.32 (s,
2), 64.51 (C-3), 21.62 (C-Me) ppm. IR (KBr): ν = 3389 (OH), 2919 9 H, tBu) ppm. 13C NMR (75.5 MHz, CDCl3): δ = 151.0 (C-4a),
˜
(C–H), 736 (Ar–Me), 1666 (C=C) cm–1. UV (CH3CN): λmax (lgε) = 141.2 (C-1Ј), 131.9 (C-1), 130.2 (C-10a), 129.0(C-6), 128.6 (C-6a),
364.5 (3.828), 380.0 (3.926), 323.0 (3.850), 309.0 (3.761), 245.5 nm
(4.274). MS (70 eV, EI): m/z (%) = 300.1 (100) [M]+, 283.1 (94)
[M – OH]+, 239.1 (44) [C19H11]+. C21H16O2 (300.36): calcd.
300.1150; found 300.1150.
128.5 (C-7), 126.3 (C-9), 123.6 (C-10), 123.2 (C-8), 117.9 (C-5),
114.4 (C-10b), 72.02 (C-3), 62.55 (C-2), 33.44 (C-2Ј), 31.56 (3×C-
2Ј Me) ppm. IR (KBr): ν = 3383 (OH), 2958 (C–H), 1595 (C=C),
˜
1467 (CH2), 1231 (Ar–O), 1075 (CH2–O) cm–1. UV (CH3CN): λmax
Eur. J. Org. Chem. 2006, 4676–4684
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
4683

L. F. Tietze, F. Lotz
FULL PAPER
Stimulating Concepts in Chemistry (Eds.: M. Shibasaki, J. F.
Stoddart, F. Vögtle), Wiley-VCH, Weinheim, 2000, 39–64; e)
G. Poli, G. Giambastiani, A. Heumann, Tetrahedron 2000, 56,
5959–5989.
(lgε) = 346.0 (3.649), 333.5 (3.599), 301.0 (3.685), 289.5 (3.746),
278.5 (3.701), 240.5 nm (4.564). MS (70 eV, EI): m/z (%) = 268.1
(56) [M]+, 253.1 (10) [C18H21O]+, 195.1 (32) [C14H11O]+, 181.0 (38)
[C13H9O]+. C18H20O2 (268.36): calcd. 268.1463; found 268.1463.
[2] L. F. Tietze, K. Kahle, T. Raschke, Chem. Eur. J. 2002, 8, 401–
407.
Synthesis of 16 by Elimination of Water from 5: A solution of 5 in
CHCl3 was kept for 10 h at room temp. Removal of the solvent in
vacuo gave 16.
[3] M. K. J. ter Wiel, B. L. Feringa, Synthesis 2005, 11, 1789–1796.
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38, 1698–1712; b) C. Jia, T. Kitamura, Y. Fujiwara, Acc. Chem.
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pin, Chem. Rev. 1997, 97, 2879–2932; e) H. M. L. Davies,
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Echavarren, J. Am. Chem. Soc. 2006, 128, 1066–1067; b) A. J.
Mota, A. Dedieu, C. Bour, J. Suffert, J. Am. Chem. Soc. 2005,
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1
4-(2-Phenoxyphenyl)-1-oxacyclopenta[def]phenanthrene (16a): H
NMR (600 MHz, CDCl3): δ = 8.23 (d, J = 7.2 Hz, 1 H, 10-H),
8.11 (d, J = 8.8 Hz, 1 H, 6-H*), 7.99 (d, J = 7.9 Hz, 1 H, 7-H*),
7.87 (dd, J = 7.9, 7.3 Hz, 1 H, 9-H*), 7.57 (d, J = 8.8 Hz, 1 H, 5-
H*), {7.87–7.90 (m, 1 H), 7.58 (d, J = 4.8 Hz, 1 H), 7.28–7.34 (m,
2 H), 7.12–7.19 (m, 4 H), 6.90–6.96 (m, 3 H), (2-H, 3-H, 8-H, 1Ј-
H, 2Ј-H, 3Ј-H, 4Ј-H, 5Ј-H, 6Ј-H, 7Ј-H, 8Ј-H)} ppm. C26H16O2
+
H+ (361.41): calcd. 361.12231, found 361.12233.
1
4-(4-Methoxyphenyl)-1-oxacyclopenta[def]phenanthrene (16b): H
NMR (200 MHz, CDCl3): δ = 8.23 (d, J = 7.1 Hz, 1 H, 5-H), 8.14
(d, J = 8.9 Hz, 1 H, 8-H), 8.05 (d, J = 7.9 Hz, 1 H, 7-H), 7.90 (dd,
J = 7.9, 7.1 Hz, 1 H, 6-H), 7.84 (mc, 2 H, 3Ј-H, 5Ј-H), 7.61 (d, J =
8.9 Hz, 1 H, 9-H), 7.58 (d, J = 6.0 Hz, 1 H, 2-H), 7.15 (d, J = 6.0,
1 H, 3-H), 7.10 (mc, 2 H, 2Ј-H, 6Ј-H), 3.91 (s, 1 H, Me) ppm.
C21H14O2 (298.34): calcd. 298.0994, found 298.0994.
Acknowledgments
This research project was supported by the Fonds der Chemischen
Industrie.
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Received: May 15, 2006
Published Online: August 22, 2006
4684
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© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2006, 4676–4684