Efficient activation of aromatic C-H bonds for fused polyaromatic hydrocarbon construction

Article abstract of DOI:10.1002/chem.201000672

An extraordinary domino method for the construction of polycyclic aromatic hydrocarbons has been established. Various 4,9-diphenyl-2,3-dihydro-1H- cyclopenta[b]naphthalene derivatives are constructed by the palladium(0)- catalyzed reaction of diynes with

Full text of DOI:10.1002/chem.201000672

FULL PAPER
DOI: 10.1002/chem.201000672
À
Efficient Activation of Aromatic C H Bonds for Fused Polyaromatic
Hydrocarbon Construction
Yimin Hu,* Hao Yao, Yongjie Sun, Jing Wan, Xiangang Lin, and Tao Zhu[a]
Abstract: An extraordinary domino method for the construction of polycyclic aro-
matic hydrocarbons has been established. Various 4,9-diphenyl-2,3-dihydro-1H-cy-
clopenta[b]naphthalene derivatives are constructed by the palladium(0)-catalyzed
À
Keywords: 1,6-diynes · C H activa-
tion · domino reactions · palladium ·
polyaromatic hydrocarbons
À
reaction of diynes with aryl halides through C–C coupling and C H bond activa-
tion of the incorporated aryl group, which provides an effective p-system synthesis.
Introduction
tivities are often excellent and a complex structure can be
accessed through a sequence of carbon–carbon bond-form-
ing reactions. Given the value of the products and the po-
tential efficiency with which they can be prepared by the
use of this method, our observations should enable further
development of industrially important PAH[10] molecules.
Herein, we report a novel domino cyclization for the prepa-
ration of an assortment of 4,9-diphenyl-2,3-dihydro-1H-cy-
clopenta[b]naphthalene derivatives from 1,6-diynes and aryl
halides. The cascade consists of inter-intramolecular Heck
reaction and subsequent regioselective direct arylation by
Polyaromatic hydrocarbons (PAHs) possess semiconducting
properties that permit their implementation in electronic de-
vices.[1] The chemical flexibility of the organic emitters and
their low production cost make them ideal materials for
spintronics applications.[2] An important feature of organic
electroluminescence is that the charge mobility increases
with the number of p-conjugated fused rings.[3] Domino re-
actions have been established as a powerful tool to accom-
plish this goal because they offer highly efficient transforma-
tions and allow the build up of complex structures over
fewer steps with increased overall yields.[4–6] Additionally,
À
C H activation of the introduces aryl group (Scheme 1). In
a typical procedure, a mixture of diethyl 2,2-bis(3-phenyl-
À
Pd-catalyzed olefination of aryl C H bonds is a potentially
powerful platform for a more direct access to carbogenic
cores of complex molecules.[7] The first examples of success-
ful intramolecular-Heck direct arylation via alkyl PdII inter-
mediates have recently been reported.[8,9]
Therefore, we reasoned that the development of new ap-
proaches to the synthesis of structurally diverse scaffolds
would likely benefit from metal-catalyzed domino inter-in-
tramolecular reactions. The inter-intramolecular nature of
these transformations means that the regio- and stereoselec-
[a] Prof. Dr. Y. Hu, H. Yao, Y. Sun, J. Wan, X. Lin, T. Zhu
Laboratory of Functional Molecular Solids, Ministry of Education
Anhui Key Laboratory of Functional Molecular-Based Materials
Institute of Organic Chemistry
School of Chemistry and Materials Science
Anhui Normal University, Wuhu, Anhui 241000 (China)
Fax : (+86)553-388-3517
E-mail: yiminhu@mail.ahnu.edu.cn
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201000672.
Scheme 1. Construction of the p system of the PAH core.
Chem. Eur. J. 2010, 16, 7635 – 7641
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
7635

Table 1. The palladium-catalyzed, one-pot reaction for the formation of fused PAHs.[a,b]
3aa (76%)
3ab (78%)
3ac (60%)
3ad (87%)
3ae (77%)
3af (70%)
3ba (73%)
3bb (72%)
3bc (84%)
3bd (79%)
3be (59%)
3ea (62%)
3 fb (81%)
3ca (78%)
3eb (76%)
3 fc (83%)
3cb (75%)
3ec1 (38%)
3 fd (77%)
3da (80%)
3ed1 (35%)
3ec2 (49%)
3db (85%)
3 fa (77%)
3ed2 (52%)
[a] Conditions: Substrate 1a–f (1.0 equiv), R2C6H4X (1.2 equiv), Pd
ACHTNUGTRNE(UNG OAc)2 (2 mol%), PPh3 (4 mol%), nBu3N (2 equiv), DMF (10 mL), 110–1158C, 20 h.
[b] Yield given for isolated product.
prop-2-ynyl)malonate (1a), 4-bromobenzonitrile, tributyl-
amine, and Pd(OAc)2 was heated in DMF under argon over-
night. Standard workup procedures afforded the coupled
most diynes (Table 1). The temperature is crucial for this re-
action; no domino reaction occurred below 908C. In con-
trast, higher reaction temperatures (>1208C) led to the de-
composition of 3ad, as indicated by TLC. Reactions that
G
ACHTUNGTRENNUNG
products 3 with excellent regio- and stereoselectivity for
7636
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Chem. Eur. J. 2010, 16, 7635 – 7641

Fused Polyaromatic Hydrocarbon Construction
FULL PAPER
employed other phosphine compounds, such as PACTHUNRGTNEUNG(OMe)3, P-
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
A
N
CHTUNGTRENNUNG
A
N
G
CHTUNGTRENNUNG
was the most effective. DMF was found to be a better sol-
vent than N,N-dimethylacetamide, toluene, dioxane, or
CH3CN for this reaction. nBu3N was more effective than
any of the inorganic bases (K2CO3, Cs2CO3) tested. Thus,
the following standard reaction conditions were selected for
the following studies: diyne (1 equiv) was treated with aryl
Figure 1. ORTEP plot of 3ab, shows ellipsoids at the 30% probability
À
level. Selected bond lengths [ꢁ] and angles [8]: C(9) C(10) 1.384(2),
halide (1.2 equiv) in the presence of PdACTHNURTGNENG(U OAc)2 (2 mol%),
PPh3 (4 mol%), and nBu3N (2 equiv) in DMF at 1108C.
À
À
À
C(9) C(22) 1.400(3), C(10) C(11) 1.427(4), C(11) C(20) 1.425(4),
À
À
C(20) C(21) 1.430(4), C(21) C(22) 1.380(4); C(9)-C(10)-C(30) 120.9(2),
C(11)-C(10)-C(30) 121.0(2), C(20)-C(21)-C(24) 124.6(2), C(22)-C(21)-
C(24) 116.6(2).
Results and Discussion
Illustrative examples of the scope of the reaction are shown
in Table 1. A variety of diynes and substituted aryl halides
are compatible with this palladium-catalyzed domino reac-
tion. A range of 4,9-diphenyl-2,3-dihydro-1H-cyclopenta[b]-
naphthalene derivatives were readily isolated in good to ex-
cellent yields, except in the case of 3ec1 and 3ed1, when aryl
halides with a variety of substituted groups were employed.
The aryl substituents could be ethoxycarbonyl, keto, naph-
thalenyl, cyano, or formacyl groups. Reaction of 4-bromo-
benzonitrile with 1a or 1 f and of 1-(4-bromophenyl)etha-
none with 1d and 1 f afforded 3,3-disubstituted 2,3-dihydro-
1H-cyclopenta[b]naphthalenes 3ad, 3 fc, 3db, and 3 fb, re-
spectively, in yields beyond 83%. The yield of compound
3ad was the highest, at 87%. When 1-bromonaphthalene
was used in the reaction with 1a, 1e, or 1 f, the desired
PAHs 3ab, 3eb, and 3 fa were obtained in very good yields,
from 76–78%.
in the Supporting Information (see also the Experimental
Section).
A plausible mechanism for the cross-coupling reaction is
depicted in Scheme 2. Coordination and insertion of arylpal-
ladium(II) halide to the diyne moiety (1) produces the inter-
ꢀ
mediate A, which then reacts with the second C C triple
bond through a carbopalladation reaction to afford B. A s-
bond metathesis[13] with the aryl group in B, followed by a
proton abstraction by the base generates 3.
To discover the reactivity with broadly useful substrates
for preparing PAHs, in which all the moieties present in the
starting material can be used for the subsequent synthetic
applications in an atom-economical manner, we chose 1,7-
bis(4-chlorophenyl)hepta-1,6-diynes 1d–f as the coupling
À
partners. Interestingly, it was found that only the C Br bond
reacted with the 1,6-diynes when bromine and chlorine sub-
stituents were both present on the benzene ring. The out-
puts of the reaction of non-chlorinated substrates 1a–c were
close to those of substrates 1d–f. These results demonstrate
Scheme 2. Proposed mechanism for the domino reaction.
À
that an aryl-C Cl group can be incorporated into the PAHs
Conclusion
as a synthetic handle for further functionalization. However,
the cyclic compounds 3ec1 and 3ed1 had low yields
(Table 1), 38 and 35%, respectively. This is probably be-
cause of deoxycarbonyl decomposition of the desired prod-
ucts to give 3ec2 and 3ed2.[11]
We have developed a palladium-catalyzed domino reaction
for the synthesis of fused polycyclic hydrocarbons through
À
À
multistep C C bond formation and C H activation of the
incorporated aryl group by treatment of diynes with a varie-
ty of aryl halides. This affords diphenylcyclopentanaphtha-
lene derivatives in moderate to very good yields and with
excellent regioselectivities. In addition to synthetic utility,
the demonstrated ability to combine direct arylation into
this class of tandem process raises confidence in the viability
All new products were fully characterized by various
spectroscopic techniques (1H, 13C NMR, UV, and IR spec-
troscopies, and HRMS). The molecular structure and rela-
tive configuration of 3ab were confirmed unambiguously by
X-ray diffraction (Figure 1).[12] Further details can be found
Chem. Eur. J. 2010, 16, 7635 – 7641
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
7637

Y. Hu et al.
713, 704, 526 cmÀ1; UV/Vis (CH3CN): lmax =260 nm; HRMS (EI): m/z:
calcd for C35H30O4: 514.2144; found: 514.2141. CCDC-764193 contains
the supplementary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_ request/cif.
of other domino processes involving alkylpalladium(II) reac-
tive intermediates. This provides a new methodology for the
synthesis of fused p-conjugated polycyclic hydrocarbons.
Further investigation to understand this catalytic transfor-
mation, evaluation of the process with a broader scope of
substrates, synthesis of more complex p-system products,
and the development of functional organic materials are in
progress.
Compound 3ac: White solid; 296 mg (60%); Rf =0.42 (petroleum ether/
EtOAc=10:1); m.p. 78–798C; 1H NMR (300 MHz, CDCl3): d=9.96 (s,
1H; -CHO), 8.12 (s, 1H; Ar-H), 7.79 (d, J=8.1 Hz, 1H; Ar-H), 7.72 (d,
J=9.0, 1H; Ar-H), 7.10–7.37 (m, 5H; Ar-H), 7.40–7.67 (m, 5H; Ar-H),
4.16 (q, J=6.6 Hz, 4H; CH3CHH-), 3.57 (s, 4H; -CHH-), 1.20 ppm (t, J=
7.2 Hz, 6H; CH3-); 13C NMR (75 MHz, CDCl3): d=192.5, 171.2, 140.8,
138.4, 138.0, 133.4, 133.0, 129.8, 129.8, 128.8, 128.8, 128.0, 127.7, 127.1,
121.9, 61.8, 60.2, 40.6, 40.2, 14.0 ppm; IR (neat): v˜ =1732, 1694, 1260,
1259, 1186, 752, 702, 518 cmÀ1; UV/Vis (CH3CN): lmax =265 nm; HRMS
(EI): m/z: calcd for C32H28O5: 492.1937; found: 492.1938.
Experimental Section
General: All the catalytic reactions were performed under an argon at-
mosphere using oven-dried Schlenk flasks. Chemicals were purchased
from Alfa Aesar and Acros Chemicals. All solvents and materials were
dried, distilled, or recrystallized before use. 1H (300 MHz) and 13C NMR
(75 MHz) spectra were recorded on a Bruker Avance 300 spectrometer
with CDCl3 as the solvent. Chemical shifts (d) are reported in ppm rela-
Compound 3ad: White solid; 426 mg (87%); Rf =0.42 (petroleum ether/
EtOAc=10:1); m.p. 142–1438C; H NMR (300 MHz, CDCl3): d=8.02 (s,
1
1H; Ar-H), 7.70 (d, J=8.1 Hz, 1H; Ar-H), 7.57 (d, J=6.0 Hz, 1H; Ar-
H), 7.27–7.39 (m, 5H; Ar-H), 7.41–7.54 (m, 5H; Ar-H), 4.15 (q, J=
6.6 Hz, 4H; CH3CHH-), 3.56 (s, 4H; CHH), 1.20 ppm (t, J=6.9 Hz, 6H;
CH3); 13C NMR (75 MHz, CDCl3): d=171.1, 140.7, 139.0, 137.6, 137.2,
135.2, 134.9, 133.7, 132.3, 131.5, 129.7, 129.0, 128.8, 128.4, 128.0, 127.9,
127.2, 125.7, 119.6, 108.5, 61.8, 40.5, 40.3, 14.0 ppm; IR (neat): v˜ =1726,
1595, 1274, 1255, 1161, 1070, 829 cmÀ1; UV/Vis (CH3CN): lmax =238 nm;
HRMS (EI): m/z: calcd for C32H27NO4: 489.1940; found: 489.1943.
1
tive to TMS (d=0.00 ppm) or CDCl3 (d=77.0 ppm) for H and 13C NMR
spectra, respectively. All coupling constants (J) are reported in Hz.
Column chromatography was performed on silica gel (300–400 mesh).
Melting points were determined by using a Gallenkamp melting-point
apparatus and are uncorrected. The FTIR spectra were recorded in the
4000–400 cmÀ1 range on a Nicolet 5DX spectrometer as KBr discs or as
thin films from CHCl3 on NaCl windows. All HRMS spectra were record-
ed by EI at 70 eV. X-ray diffraction data of 3ab was collected at room
temperature with a Bruker SMART Apex CCD diffractometer using
MoKa radiation (l=0.71073 ꢁ) with a graphite monochromator using the
w-scan mode. Data reductions and absorption corrections were per-
formed with SAINT and SADABS software, respectively.[14] The structure
was solved by direct methods and refined on F2 by full-matrix least
squares using SHELXTL.[15] All non-hydrogen atoms were treated aniso-
tropically. The positions of hydrogen atoms were generated geometrical-
ly. 1,6-Diynes 1a–1 f were prepared by published procedures.[16]
Compound 3ae: White solid; 402 mg (77%); Rf =0.42 (petroleum ether/
1
EtOAc=10:1); m.p. 143–1448C; H NMR (300 MHz, CDCl3): d=8.40 (s,
1H; Ar-H), 7.88 (d, J=8.4 Hz, 1H; Ar-H), 7.66 (d, J=8.7 Hz, 1H; Ar-
H), (d, J=8.7 Hz, 1H; Ar-H), 7.29–7.42 (m, 5H; Ar-H), 7.45–7.56 (m,
5H; Ar-H), 4.14 (q, J=6.9 Hz, 4H; CH3CHH-), 3.86 (s, 3H; CH3-O),
3.55 (s, 4H; -CHH-), 1.19 ppm (t, J=6.9 Hz, 6H; CH3-); 13C NMR
(75 MHz, CDCl3): d=171.3, 167.4, 139.7, 138.2, 137.9, 136.0, 134.5, 131.5,
129.9, 129.9, 128.9, 128.7, 128.7, 127.7, 127.6, 126.7, 126.2, 124.8, 61.7,
60.3, 52.1, 40.5, 40.3, 14.0 ppm; IR (neat): v˜ =1730, 1710, 1441, 1364,
1263, 1236, 1188, 758, 704, 516 cmÀ1; UV/Vis (CH3CN): lmax =248 nm;
HRMS (EI): m/z: calcd for C33H30O6: 522.2042; found: 522.2043.
Compound 3af: White solid; 355 mg (70%); Rf =0.43 (petroleum ether/
EtOAc=10:1); m.p. 141–1428C; H NMR (300 MHz, CDCl3): d=8.27 (s,
Typical procedure for the palladium-catalyzed domino reaction of 1,6-
diynes with aryl halides: Diyne 1a–f (1.0 equiv), 4-bromobenzonitrile
1
1H; Ar-H), 7.72 (d, J=8.4 Hz, 1H; Ar-H), 7.68 (d, J=8.7 Hz, 1H; Ar-
H), 7.27–7.38 (m, 5H; Ar-H), 7.40–7.58 (m, 5H; Ar-H), 4.14 (q, J=
6.9 Hz, 4H; CH3CHH-O-), 3.56 (s, 4H; -CHH-), 2.50 (s, 3H; -CO-CH3),
1.20 ppm (t, J=6.6 Hz, 6H; CH3-); 13C NMR (75 MHz, CDCl3): d=
198.3, 171.3, 140.0, 138.1, 138.0, 137.9, 136.2, 134.7, 134.5, 133.8, 131.5,
129.9, 129.8, 128.7, 128.7, 128.2, 127.8, 127.6, 126.4, 123.1, 112.7, 61.8,
60.3, 40.5, 40.3, 26.5, 14.0 ppm; IR (neat): v˜ =1734, 1684, 1602, 1257,
1234, 1190, 1072, 750, 704 cmÀ1; UV/Vis (CH3CN): lmax =259 nm; HRMS
(EI): m/z: calcd for C33H30O5: 506.2093; found: 506.2092.
(1.2 equiv), PdACHTUNGTRENNUNG(OAc)2 (2 mol%), and PPh3 (4 mol%) were added to a de-
gassed solution of nBu3N (2 equiv) in DMF (5 mL). The mixture was
stirred at room temperature for 30 min then heated at 110–1158C for
20 h. The reaction mixture was cooled, quenched with water, and extract-
ed with EtOAc (3ꢂ5 mL). The combined organic layers were washed
with hydrochloric acid (5%), aqueous sodium carbonate (5%), and satu-
rated aqueous sodium chloride solution. After separation, the organic
layer was dried over anhydrous MgSO4 and concentrated under reduced
pressure. The residue was purified by flash column chromatography (10:1
petroleum ether/EtOAc) to give the corresponding product 3.
Compound 3ba: Yellow oil; 349 mg (73%); Rf =0.44 (petroleum ether/
EtOAc=8:1); 1H NMR (300 MHz, CDCl3): d=8.28 (s, 1H; Ar-H), 7.87
(d, J=8.7 Hz, 1H; Ar-H), 7.69 (d, J=8.7 Hz, 1H; Ar-H), 7.27–7.38 (m,
5H; Ar-H), 7.40–7.58 (m, 5H; Ar-H), 3.70 (s, 6H; CH3O-), 3.58 (s, 4H;
-CHH-), 2.50 ppm (s, 3H; -OCCH3); 13C NMR (75 MHz, CDCl3): d=
198.2, 171.7, 139.7, 138.0, 137.9, 137.8, 134.7, 134.5, 133.8, 131.6, 129.9,
129.8, 128.7, 128.7, 128.5, 128.2, 127.8, 127.7, 127.1, 126.4, 123.2, 60.1,
53.0, 40.6, 40.4, 26.5 ppm; IR (neat): v˜ =1736, 1681, 1435, 1365, 1259,
1236, 752, 702, 516 cmÀ1; UV/Vis (CH3CN): lmax =261 nm; HRMS (EI):
m/z: calcd for C31H26O5: 478.1780; found: 478.1781.
Compound 3aa: White solid; 408 mg (76%); Rf =0.43 (petroleum ether/
1
EtOAc=10:1); m.p. 176–1778C; H NMR (300 MHz, CDCl3): d=8.40 (s,
1H; Ar-H), 7.88 (d, J=9.0 Hz, 1H; Ar-H), 7.66 (d, J=9.0 Hz, 1H; Ar-
H), 7.29–7.42 (m, 5H; Ar-H), 7.43–7.55 (m, 5H; Ar-H), 4.32 (q, J=
6.6 Hz, 2H; CH3CHH-), 4.16 (q, J=6.3 Hz, 4H; CH3CHH-), 3.55 (s, 4H;
-CHH-), 1.34 (t, J=6.9 Hz, 3H; CH3-), 1.19 ppm (t, J=6.9 Hz, 6H; CH3-);
13C NMR (75 MHz, CDCl3): d=171.3, 166.9, 139.6, 138.3, 138.0, 137.8,
136.0, 134.6, 134.4, 131.6, 129.9, 129.9, 128.9, 128.7, 127.7, 127.6, 127.0,
126.1, 124.5 , 61.7, 60.9, 60.3, 40.4, 40.3, 14.2, 14.0 ppm; IR (neat): v˜ =
1732, 1714, 1275, 1238, 1072, 704, 519 cmÀ1; UV/Vis (CH3CN): lmax
=
Compound 3bb: White solid; 366 mg (72%); Rf =0.43 (petroleum ether/
1
252 nm; HRMS (EI): m/z: calcd for C34H32O6: 536.2199; found: 536.2198.
EtOAc=10:1); m.p. 142–1438C; H NMR (300 MHz, CDCl3): d=8.42 (s,
1H; Ar-H), 8.23 (d, J=7.2 Hz, 1H; Ar-H), 7.90 (d, J=8.4 Hz, 1H; Ar-
H), 7.27–7.45 (m, 5H; Ar-H), 7.49–7.68 (m, 5H; Ar-H), 4.32(q, J=7.2 Hz,
2H; CH3CHH-O-), 3.69 (s, 6H; CH3-), 3.57 (s, 4H; -CHH-), 1.33 ppm (t,
J=6.9 Hz, 3H; CH3-); 13C NMR (75 MHz, CDCl3): d=171.7, 166.9,
138.2, 137.6, 130.1, 130.0, 129.9, 128.9, 128.7, 128.6, 27.7, 127.6, 127.4,
127.1, 126.1, 126.1, 125.5, 125.5, 125.4, 124.6, 60.9, 60.2, 53.0, 40.4, 40.3,
Compound 3ab: White solid; 401 mg (78%); Rf =0.42 (petroleum ether/
EtOAc=10:1); m.p. 128–1298C; 1H NMR (300 MHz, CDCl3): d=7.76
(d, J=7.8 Hz, 1H; Ar-H), 7.68 (d, J=8.7 Hz, 1H; Ar-H), 7.03–7.18 (m,
4H; Ar-H), 7.20–7.38 (m, 5H; Ar-H), 7.41–7.58 (m, 5H; Ar-H), 4.15 (q,
J=7.2 Hz, 4H; CH3CHH-), 3.53 (d, J=18 Hz, 4H; -CHH-), 1.20 ppm (t,
J=7.2 Hz, 6H; CH3-); 13C NMR (75 MHz, CDCl3): d=171.2, 143.3,
139.4, 139.2, 137.2, 135.4, 132.9, 131.6, 130.1, 130.0, 129.6, 128.9, 128.6,
128.2, 128.1, 127.3, 127.2, 126.8, 125.6, 124.9, 114.9, 61.7, 60.1, 41.3, 40.1,
14.0 ppm; IR (neat): v˜ =1726, 1493, 1442, 1274, 1244, 1193, 1072, 750,
14.3 ppm; IR (neat): v˜ =1732, 1713, 1618, 1263, 1238, 756, 706, 517 cmÀ1
;
UV/Vis (CH3CN): lmax =272 nm; HRMS (EI): m/z: calcd for C32H28O6:
508.1886; found: 508.1884.
7638
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Chem. Eur. J. 2010, 16, 7635 – 7641

Fused Polyaromatic Hydrocarbon Construction
FULL PAPER
Compound 3bc: White solid; 409 mg (84%); Rf =0.44 (petroleum ether/
EtOAc=10:1); m.p. 174–1758C; 1H NMR (300 MHz, CDCl3): d=7.77
(d, J=7.5 Hz, 1H; Ar-H), 7.68 (d, J=7.8 Hz, 1H; Ar-H), 7.07–7.25 (m,
5H; Ar-H), 7.28–7.39 (m, 5H; Ar-H), 7.42–7.57 (m, 4H; Ar-H), 3.70 (s,
6H; CH3-O-), 3.56 ppm (d, J=19.0 Hz, 4H; -CHH-); 13C NMR (75 MHz,
CDCl3): d=172.0, 143.2, 139.3, 139.0, 137.0, 135.7, 135.4, 133.0, 131.2,
130.1, 130.0, 129.6, 129.0, 128.6, 128.2, 128.1, 127.4, 127.3, 126.8, 125.7,
124.9, 59.9, 52.9, 41.5, 40.7 ppm; IR (neat): v˜ =1732, 1489, 1435, 1277,
6.9 Hz, 4H; CH3CHH-O-), 3.53 (s, 4H; -CHH-), 2.53 (s, 3H; -CO-CH3),
1.20 ppm (t, J=6.9 Hz, 6H; CH3-); 13C NMR (75 MHz, CDCl3): d=
198.1, 171.1, 140.1, 138.2, 136.4, 136.2, 135.2, 134.3, 134.0, 133.2, 133.7,
131.4, 131.2, 131.2, 129.1, 129.1, 127.7, 126.3, 123.6, 119.4, 61.9, 60.3, 40.4,
40.2, 26.7, 14.0 ppm; IR (neat): v˜ =1732, 1682, 1491, 1367, 1258, 1236,
1188, 1091, 819, 524 cmÀ1; UV/Vis (CH3CN): lmax =277 nm; HRMS (EI):
m/z: calcd for C33H28Cl2O5: 574.1314; found: 574.1311.
Compound 3ea: White solid; 339 mg (62%); Rf =0.42 (petroleum ether/
EtOAc=8:1); m.p. 135–1368C; 1H NMR (300 MHz, CDCl3): d=8.24 (s,
1H; Ar-H), 7.89 (d, J=8.7 Hz, 1H; Ar-H), 7.66 (d, J=8.7 Hz, 1H; Ar-
H), 7.55 (s, 4H; Ar-H), 7.35 (d, J=8.1 Hz, 4H; Ar-H), 3.71 (s, 6H; CH3-
O-), 3.55 (s, 4H; -CHH-), 2.53 ppm (s, 3H; -CO-CH3); 13C NMR
(75 MHz, CDCl3): d=198.2, 171.5, 139.9, 138.0, 136.3, 136.1, 135.2, 134.3,
134.1, 134.0, 133.9, 133.7, 131.4, 131.2, 131.2, 129.1, 129.1, 127.7, 126.3,
123.7, 60.0, 53.1, 40.5, 40.3, 26.6 ppm; IR (neat): v˜ =1739, 1680, 1610,
1242, 1159, 1072, 873, 752, 715, 702, 527 cmÀ1; UV/Vis (CH3CN): lmax
=
260 nm; HRMS (EI): m/z: calcd for C33H26O4: 486.1831; found: 486.1834.
Compound 3bd: White solid; 365 mg (79%); Rf =0.45 (petroleum ether/
1
EtOAc=10:1); m.p. 195–1968C; H NMR (300 MHz, CDCl3): d=8.02 (s,
1H; Ar-H), 7.72 (d, J=9.0 Hz, 1H; Ar-H), 7.57 (d, J=5.71 Hz, 1H; Ar-
H), 7.27–7.40 (m, 5H; Ar-H), 7.42–7.54 (m, 5H; Ar-H), 3.70 (s, 6H;
CH3-O-), 3.56 ppm (s, 4H; -CHH-); 13C NMR (75 MHz, CDCl3): d=
171.5, 140.4, 138.7, 137.4, 137.1, 135.2, 133.7, 132.2, 131.5, 129.7, 129.2,
128.9, 128.8, 128.4, 128.0, 127.9, 127.3, 127.2, 125.7, 119.5, 108.5, 59.9,
53.0, 40.5, 40.3 ppm; IR (neat): v˜ =2226, 1734, 1433, 1280, 1259, 1205,
1076, 752, 704 cmÀ1; UV/Vis (CH3CN): lmax =250 nm; HRMS (EI): m/z:
calcd for C30H23NO4: 461.1627; found: 461.1623.
1490, 1256, 1091, 1012, 841, 822, 609, 525 cmÀ1; UV/Vis (CH3CN): lmax
=
256 nm; HRMS (EI): m/z: calcd for C31H24Cl2O5: 546.1001; found:
546.0999.
Compound 3eb: White solid; 422 mg (76%); Rf =0.44 (petroleum ether/
EtOAc=10:1); m.p. 242–2438C; 1H NMR (300 MHz, CDCl3): d=7.78
(d, J=7.8 Hz, 1H; Ar-H), 7.69 (d, J=8.4 Hz, 1H; Ar-H), 7.13–7.55 (m,
12H; Ar-H), 3.71 (s, 6H; CH3-O-), 3.51 ppm (d, J=19.8 Hz, 4H; -CHH-);
13C NMR (75 MHz, CDCl3): d=171.8, 142.2, 139.4, 139.1, 137.0, 135.7,
135.4, 133.0, 131.1, 130.4, 130.1, 129.6, 129.0, 128.6, 128.2, 128.1, 127.4,
127.3, 126.8, 123.7, 124.9, 59.9, 52.8, 41.5, 40.6 ppm; IR (neat): v˜ =1736,
1492, 1429, 1281, 1250, 1152, 1091, 1072, 808, 750, 529 cmÀ1; UV/Vis
(CH3CN): lmax =265 nm; HRMS (EI): m/z: calcd for C33H24Cl2O4:
554.1052; found: 554.1056.
Compound 3be: White solid; 274 mg (59%); Rf =0.45 (petroleum ether/
EtOAc=10:1); m.p. 79–808C; 1H NMR (300 MHz, CDCl3): d=9.96 (s,
1H; -CHO), 8.13 (s, 1H; Ar-H), 7.80 (d, J=8.7 Hz, 1H; Ar-H), 7.74 (d,
J=8.7 Hz, 1H; Ar-H), 7.09–7.37 (m, 5H; Ar-H), 7.39–7.59 (m, 5H; Ar-
H), 3.70 (s, 6H; CH3-O-), 3.59 ppm (s, 4H; -CHH-); 13C NMR (75 MHz,
CDCl3): d=192.5, 171.7, 142.7, 140.5, 138.2, 137.9, 137.7, 135.4, 135.1,
133.4, 132.9, 129.8, 129.8, 129.3, 128.9, 128.8, 128.5, 128.3, 128.0, 127.8,
127.1, 121.9, 60.0, 53.0, 40.7, 40.4 ppm; IR (neat): v˜ =1734, 1693, 1614,
1602, 1435, 1263, 1203, 1072, 831, 752, 702, 519 cmÀ1; UV/Vis (CH3CN):
lmax =269 nm; HRMS (EI): m/z: calcd for C30H24O5: 464.1624; found:
464.1621.
Compound 3ec1: White solid; 219 mg (38%); Rf =0.44 (petroleum ether/
1
EtOAc=10:1); m.p. 164–1658C; H NMR (300 MHz, CDCl3): d=8.37 (s,
1H; Ar-H), 7.92 (d, J=8.4 Hz, 1H; Ar-H), 7.64 (d, J=8.7 Hz, 1H; Ar-
H), 7.27–7.55 (m, 8H; Ar-H), 4.34 (q, J=6.6 Hz, 2H; CH3-CHH-O-),
3.71 (s, 6H; CH3-O-), 3.54 (s, 4H; -CHH-), 1.35 ppm (t, J=6.6 Hz, 3H;
-CH3); 13C NMR (75 MHz, CDCl3): d=171.5, 166.6, 139.4, 137.7, 136.3,
136.1, 135.0, 134.2, 133.8, 133.7, 133.6, 131.3, 131.2, 131.1, 129.0, 128.5,
127.3, 125.9, 124.9, 61.0, 60.0, 53.0, 40.4, 40.3, 14.2 ppm; IR (neat): v˜ =
1738, 1709, 1492, 1269, 1259, 1096, 1014, 824, 761, 524 cmÀ1; UV/Vis
(CH3CN): lmax =251 nm; HRMS (EI): m/z: calcd for C32H26Cl2O6:
576.1106; found: 576.1102.
Compound 3ed1: White solid; 197 mg (35%); m.p. 141–1428C; Rf =0.44
(petroleum ether/EtOAc=10:1); 1H NMR (300 MHz, CDCl3): d=8.35 (s,
1H; Ar-H), 7.92 (d, J=8.7 Hz, 1H; Ar-H), 7.64 (d, J=8.7 Hz, 1H; Ar-
H), 7.27–7.54 (m, 8H; Ar-H), 3.89 (s, 3H; CH3-O-), 3.70 (s, 6H; CH3-O-),
3.54 ppm (s, 4H; -CHH-); 13C NMR (75 MHz, CDCl3): d=171.5, 167.1,
139.5, 137.8, 136.3, 136.1, 135.0, 134.3, 133.8,133.8, 133.6, 131.3, 131.2,
131.1, 130.6, 129.0, 129.0, 128.5, 127.0, 125.9, 124.9, 59.9, 53.0, 52.2, 40.4,
40.3 ppm; IR (neat): v˜ =1738, 1717, 1489, 1435, 1300, 1271, 1161, 1093,
1012, 844, 823, 763, 524 cmÀ1; UV/Vis (CH3CN): lmax =252 nm; HRMS
(EI): m/z: calcd for C31H24Cl2O6: 562.0950; found: 562.0928.
Compound 3ca: White solid; 378 mg (78%); Rf =0.45 (petroleum ether/
EtOAc=10:1); m.p. 93–948C; 1H NMR (300 MHz, CDCl3): d=7.77 (d,
J=7.5 Hz, 1H; Ar-H), 7.66 (d, J=8.7 Hz, 1H; Ar-H), 7.04–7.15 (m, 4H;
Ar-H), 7.17–7.35 (m, 5H; Ar-H), 7.38–7.55 (m, 5H; Ar-H), 4.16 (q, J=
6.9 Hz, 2H; CH3CHH-O-), 3.49 (s, 4H; -CHH-), 2.14 (s, 3H; -OCCH3),
1.21 ppm (t, J=6.6 Hz, 3H; CH3-); 13C NMR (75 MHz, CDCl3): d=
202.9, 172.3, 139.4, 137.0, 133.0, 131.7, 130.0, 129.6, 129.6, 128.9, 128.7,
128.6, 128.2, 128.1, 127.4, 127.3, 126.8, 125.7, 124.9, 124.9, 124.9, 108.0,
66.5, 61.8, 40.0, 39.2, 26.3, 14.0 ppm; IR (neat): v˜ =1712, 1598, 1490, 1440,
1355, 1070, 825, 750, 702, 667, 521 cmÀ1; UV/Vis (CH3CN): lmax =275 nm;
HRMS (EI): m/z: calcd for C34H28O3: 484.2038; found: 484.2039.
Compound 3cb: Yellow oil; 357 mg (75%); Rf =0.41 (petroleum ether/
EtOAc=8:1); 1H NMR (300 MHz, CDCl3): d=8.26 (s, 1H; Ar-H), 7.87
(d, J=8.7 Hz, 1H; Ar-H), 7.67 (d, J=8.7 Hz, 1H; Ar-H), 7.08–7.26 (m,
5H; Ar-H), 7.30–7.59 (m, 5H; Ar-H), 4.17 (q, J=6.9 Hz, 2H; CH3CHH-
O-), 3.49 (s, 4H; -CHH-), 2.50 (s, 3H; -OCCH3), 2.15 (s, 3H; -OCCH3),
1.21 ppm (t, J=6.9 Hz, 3H; CH3-); 13C NMR (75 MHz, CDCl3): d=
202.6, 198.3, 171.1, 139.9, 138.7, 138.1, 137.9, 136.3, 134.8, 134.5, 133.8,
131.6, 130.5, 129.8, 128.8, 128.2, 127.9, 127.7, 126.4, 123.2, 66.7, 62.0, 39.1,
38.9, 26.5, 26.3, 14.0 ppm; IR (neat): v˜ =1714, 1682, 1601, 1366, 1255,
1232, 754, 702 cmÀ1; UV/Vis (CH3CN): lmax =265 nm; HRMS (EI): m/z:
calcd for C32H28O5: 476.1988; found: 476.1992.
Compound 3 fa: White solid; 426 mg (77%); Rf =0.44 (petroleum ether/
EtOAc=10:1); m.p. 142–1438C; 1H NMR (300 MHz, CDCl3): d=7.78
(d, J=7.5 Hz, 1H; Ar-H), 7.78 (d, J=8.7 Hz, 1H; Ar-H), 7.13–7.40 (m,
6H; Ar-H), 7.43–7.60 (m, 6H; Ar-H), 4.18 (q, J=6.9 Hz, 2H; CH3CHH-
O-), 3.43 (d, J=17.4 Hz, 4H; -CHH-), 2.15 (s, 3H; -OCCH3), 1.22 ppm
(t, J=6.9 Hz, 3H; CH3-); 13C NMR (75 MHz, CDCl3): d=202.4, 172.0,
141.5, 139.1, 137.6, 137.1, 133.5, 133.2, 132.9, 131.5, 131.2, 130.3, 129.9,
129.0, 129.8, 129.0, 128.3, 127.9, 127.2, 125.9, 125.1, 124.4, 66.4, 61.9, 39.8,
39.0, 26.1, 13.9 ppm; IR (neat): v˜ =1741, 1714, 1489, 1232, 1092, 1072,
1015, 827, 766, 524 cmÀ1; UV/Vis (CH3CN): lmax =207 nm; HRMS (EI):
m/z: calcd for C34H26Cl2O3: 552.1259; found:552.1251.
Compound 3da: White solid; 467 mg (80%); Rf =0.45 (petroleum ether/
EtOAc=10:1); m.p. 94–958C; 1H NMR (300 MHz, CDCl3): d=7.79 (d,
J=7.8 Hz, 1H; Ar-H), 7.72 (d, J=8.4 Hz, 1H; Ar-H), 7.15–7.39 (m, 6H;
Ar-H), 7.41–7.61 (m, 6H; Ar-H), 4.17 (q, J=6.3 Hz, 4H; CH3CHH-O-),
3.52 (d, J=18.9 Hz, 4H; -CHH-), 1.23 ppm (t, J=6.3 Hz, 6H; CH3-);
13C NMR (75 MHz, CDCl3): d=171.3, 141.5, 139.3, 137.6, 137.3, 134.6,
134.2, 133.5, 133.2, 132.9, 131.5, 131.3, 130.4, 129.8, 128.9, 128.3, 127.9,
127.1, 125.9, 125.1, 124.4, 61.7, 60.0, 41.2, 40.4, 14.0 ppm; IR (neat): v˜ =
1742, 1717, 1489, 1473, 1250, 1178, 1089, 1012, 823, 765, 527 cmÀ1; UV/Vis
(CH3CN): lmax =276 nm; HRMS (EI): m/z: calcd for C35H28Cl2O4:
582.1365; found: 582.1361.
Compound 3 fb: White solid; 442 mg (81%); Rf =0.44 (petroleum ether/
EtOAc=8:1); m.p. 173–1748C; 1H NMR (300 MHz, CDCl3): d=8.21 (s,
1H; Ar-H), 7.88 (d, J=8.7 Hz, 1H; Ar-H), 7.63 (d, J=9.0 Hz, 1H; Ar-
H), 7.26–7.58 (m, 8H; Ar-H), 4.18 (q, J=6.6 Hz, 2H; CH3CHH-O-), 3.46
(s, 4H; -CHH-), 2.53 (s, 3H; -OCCH3), 2.16 (s, 3H; -OCCH3), 1.22 ppm
(t, J=6.6 Hz, 3H; CH3-); 13C NMR (75 MHz, CDCl3): d=202.2, 198.0,
171.8, 139.9, 138.0, 136.4, 136.2, 135.2, 134.3, 134.1, 133.9, 133.8, 131.4,
131.2, 129.2, 129.1, 129.1, 127.6, 126.2, 123.7, 66.7, 62.0, 39.0, 38.8, 26.6,
Compound 3db: White solid; 489 mg (85%); Rf =0.45 (petroleum ether/
EtOAc=8:1); m.p. 144–1458C; 1H NMR (300 MHz, CDCl3): d=8.23 (s,
1H; Ar-H), 7.88 (d, J=8.7 Hz, 1H; Ar-H), 7.65 (d, J=9.0 Hz, 1H; Ar-
H), 7.55 (t, J=6.9, 4H; Ar-H); 7.34 (t, J=8.4 Hz, 4H; Ar-H), 4.16 (q, J=
Chem. Eur. J. 2010, 16, 7635 – 7641
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
7639

Y. Hu et al.
26.2, 14.0 ppm; IR (neat): v˜ =1712, 1681, 1491, 1364, 1253, 1092, 1012,
829, 523 cmÀ1; UV/Vis (CH3CN): lmax =262 nm; HRMS (EI): m/z: calcd
for C32H26Cl2O4: 544.1208; found: 544.1197.
[4] For multiple domino reactions, see: a) L. F. Tietze, G. Brasche, K.
Gericke, Domino Reactions in Organic Synthesis, Wiley-VCH, Wein-
heim, 2006; b) L. F. Tietze, T. Kinzel, C. Brazel, Acc. Chem. Res.
2009, 42, 367–378; c) L. F. Tietze, G. Brasche, K. M. Gericke,
Angew. Chem. 2007, 119, 3035–3036; Angew. Chem. Int. Ed. 2007,
46, 2977–2978; d) U. Beifuss, K. Goldenstein, F. Dçring, C. Leh-
mann, M. Noltemeyer, Angew. Chem. 2001, 113, 591–594; Angew.
Chem. Int. Ed. 2001, 40, 568–570.
[5] a) R. G. Bergman, Nature 2007, 446, 391–393; b) H. Li, T. P. Loh, J.
Am. Chem. Soc. 2008, 130, 7194–7195; c) G. Bojase, A. D. Payne,
A. C. Willis, M. S. Sherburn, Angew. Chem. 2008, 120, 924–926;
Angew. Chem. Int. Ed. 2008, 47, 910–912; d) S. Brandau, E. Maert-
en, K. A. Jørgensen, J. Am. Chem. Soc. 2006, 128, 14986–14991;
e) Y. Hayashi, T. Okano, S. Aratake, D. Hazelard, Angew. Chem.
2007, 119, 5010–5013; Angew. Chem. Int. Ed. 2007, 46, 4922–4925;
f) M. Kita, M. Kondo, T. Koyama, K. Yamada, T. Matsumoto, K.-H.
Lee, J.-T. Woo, D. Uemura, J. Am. Chem. Soc. 2004, 126, 4794–
4795.
Compound 3 fc: White solid; 439 mg (83%); Rf =0.43 (petroleum ether/
1
EtOAc=10:1); m.p. 174–1758C; H NMR (300 MHz, CDCl3): d=7.95 (s,
1H; Ar-H), 7.67 (d, J=8.7 Hz, 1H; Ar-H), 7.58 (d, J=6.6 Hz, 1H; Ar-
H), 7.27–7.54 (m, 8H; Ar-H), 4.17 (q, J=6.6 Hz, 2H; CH3CHH-O-), 3.45
(s, 4H; -CHH-), 2.15 (s, 3H; -OCCH3), 1.22 ppm (t, J=6.9 Hz, 3H; CH3-);
13C NMR (75 MHz, CDCl3): d=201.9, 171.6, 140.6, 138.9, 135.7, 135.3,
134.3, 134.1, 133.5, 131.9, 131.3, 131.0, 130.7, 129.3, 129.3, 129.2, 129.2,
128.6, 126.9, 126.0, 119.2, 111.4 ,108.9, 66.5, 62.1, 38.9, 38.7, 26.1,
14.0 ppm; IR (neat): v˜ =2226, 1712, 1491, 1364, 1230, 1090, 1015, 820,
518 cmÀ1; UV/Vis (CH3CN): lmax =253 nm; HRMS (EI): m/z: calcd for
C31H23Cl2NO3: 527.1055; found: 524.1042.
Compound 3 fd: White solid; 443 mg (77%); Rf =0.46 (petroleum ether/
1
EtOAc=10:1); m.p. 175–1768C; H NMR (300 MHz, CDCl3): d=8.35 (s,
1H; Ar-H), 7.92 (d, J=8.7 Hz, 1H; Ar-H), 7.62 (d, J=9.0 Hz, 1H; Ar-
H), 7.27–7.56 (m, 8H; Ar-H), 4.35 (q, J=6.6 Hz, 2H; CH3CHH-O-), 4.18
(q, J=6.9 Hz, 2H; CH3CHH-O-), 3.45 (s, 4H; -CHH-), 2.15 (s, 3H;
-OCCH3), 1.35 (t, J=6.9 Hz, 3H; CH3-), 1.22 ppm (t, J=6.9 Hz, 3H;
CH3-); 13C NMR (75 MHz, CDCl3): d=202.2, 171.8, 166.6, 139.5, 137.7,
136.4, 136.2, 135.0, 134.2, 133.8, 133.7, 133.6, 131.3, 131.1, 131.1, 129.0,
129.0, 128.5, 127.3, 125.8, 124.9, 66.6, 61.9, 61.0, 38.9, 38.8, 26.1, 14.2,
13.9 ppm; IR (neat): v˜ =1714, 1645, 1361, 1263, 1234, 1091, 1014, 819,
762, 518 cmÀ1; UV/Vis (CH3CN): lmax =251 nm; HRMS (EI): m/z: calcd
for C33H28Cl2O5: 574.1314; found: 574.1309.
[6] a) N. Halland, M. Nazarꢃ, O. Rꢄkyek, J. Alonso, M. Urmann, A. Lin-
denschmidt, Angew. Chem. 2009, 121, 7011–7014; Angew. Chem.
ˇ
Int. Ed. 2009, 48, 6879–6882; b) J. Cvengros, J. Schꢅtte, D. Chem, N.
Schlçrer, J. Neudçrfl, H. G. Schmalz, Angew. Chem. 2009, 121,
6264–6267; Angew. Chem. Int. Ed. 2009, 48, 6148–6151; c) A. Diꢃ-
guez-Vꢆzquez, C. C. Tzschucke, W. Y. Lam, S. V. Ley, Angew. Chem.
2008, 120, 216–219; Angew. Chem. Int. Ed. 2008, 47, 209–212.
[7] a) D.-H. Wang, K. M. Engle, B.-F. Shi, J.-Q. Yu, Science 2010, 327,
315–319; b) J.-J. Li, T.-S. Mei, J.-Q. Yu, Angew. Chem. 2008, 120,
6552–6555; Angew. Chem. Int. Ed. 2008, 47, 6452–6455; c) M.
Wasa, J. -Q. Yu, J. Am. Chem. Soc. 2008, 130, 14058–14059; d) J.
Zhao, M. Campo, R. C. Larock, Angew. Chem. 2005, 117, 1907–
1909; Angew. Chem. Int. Ed. 2005, 44, 1873–1875; e) P. Mauleꢇn, I.
Alonso, P. Mauleon, I. Alonso, J. C. Carretero, Angew. Chem. 2001,
113, 1331–1333; Angew. Chem. Int. Ed. 2001, 40, 1291–1293; f) P.
Mauleꢇn, A. A. Nunez, I. Alonso, J. C. Carretero, Chem. Eur. J.
2003, 9, 1511–1520; g) I. Alonso, M. Alcamꢈ, P. Mauleꢇn, J. C. Car-
retero, Chem. Eur. J. 2006, 12, 4576–4583.
[8] a) J. A. Enquist, Jr., B. M. Stoltz, Nature 2008, 453, 1228–1231;
b) R. T. Ruck, M. A. Huffman, M. M. Kim, M. Shevlin, W. V.
Kandur, I. W. Davies, Angew. Chem. 2008, 120, 4789–4792; Angew.
Chem. Int. Ed. 2008, 47, 4711–4714; c) G. Satyanarayana, C.
Maichle-Mçssmer, M. E. Maier, Chem. Commun. 2009, 1571–1573;
d) O. Renffl, D. Lapointe, K. Fagnou, Org. Lett. 2009, 11, 4560–4563.
[9] a) Y. M. Hu, C. L. Yu, D. Ren, Q. Hu, L. D. Zhang, D. Cheng,
Angew. Chem. 2009, 121, 5556–5559; Angew. Chem. Int. Ed. 2009,
48, 5448–5451; b) Y. M. Hu, Y. Ouyang, Y. Qu, Q. Hu, H. Yao,
Chem. Commun. 2009, 4575–4577; c) Y. M. Hu, Y. Qu, F. H. Wu,
J. H. Gui, Y. Wei, Q. Hu, S. W. Wang, Chem. Asian. J. 2010, 5, 309–
314; d) Y. M. Hu, F. F. Song, F. H. Wu, D. Cheng, S. W. Wang,
Chem. Eur. J. 2008, 14, 3110–3117.
Compound 3ec2: White solid; 254 mg (49%); Rf =0.46 (petroleum ether/
1
EtOAc=10:1); m.p. 171–1728C; H NMR (300 MHz, CDCl3): d=8.37 (s,
1H; Ar-H), 7.92 (d, J=8.4 Hz, 1H; Ar-H), 7.63 (d, J=8.7 Hz, 1H; Ar-
H), 7.27–7.54 (m, 8H; Ar-H), 4.36 (q, J=6.9 Hz, 2H; CH3CHH-O-), 3.68
(s, 3H; CH3-O-), 3.28 (d, J=11.8 Hz, 4H; -CHH-), 3.15 (m, 1H; -CH-),
3.12–3.16 ppm (m, 1H; -CH-); 13C NMR (75 MHz, CDCl3): d=175.0,
166.7, 141.2, 139.5, 136.7, 136.4, 134.8, 134.1, 133.7, 133.6, 133.4, 131.3,
131.2, 131.1, 131.1, 129.0, 128.8, 128.5, 127.2, 125.8, 124.7, 61.0, 52.0, 43.5,
36.1, 35.9, 14.2 ppm; IR (neat): v˜ =1735, 1362, 1262, 1254, 1090, 1013,
819, 722, 522 cmÀ1; UV/Vis (CH3CN): lmax =256 nm; HRMS (EI): m/z:
calcd for C30H24Cl2O4: 518.1052; found: 518.1047.
Compound 3ed2: White solid; 263 mg (52%); Rf =0.46 (petroleum ether/
1
EtOAc=10:1); m.p. 173–1748C; H NMR (300 MHz, CDCl3): d=8.35 (s,
1H; Ar-H), 7.92 (d, J=8.7 Hz, 1H; Ar-H), 7.64 (d, J=8.7 Hz, 1H; Ar-
H), 7.27–7.54 (m, 8H; Ar-H), 3.89 (s, 3H; CH3-O-), 3.68 (s, 3H; CH3-O-),
3.27 (d, J=12.6 Hz, 4H; -CHH-), 3.12–3.17 ppm (m, 1H; -CH-);
13C NMR (75 MHz, CDCl3): d=175.0, 167.2, 141.3, 139.5, 136.6, 136.4,
134.8, 134.1, 133.7, 133.6, 131.2, 131.1, 129.0, 129.0, 128.8, 128.8, 128.5,
126.9, 125.9, 124.8, 52.1, 52.0, 43.4, 36.3, 36.1 ppm; IR (neat): v˜ =1738,
1713, 1645, 1634, 1493, 1435, 1261, 1089, 1012, 819, 763, 717, 524 cmÀ1
;
UV/Vis (CH3CN): lmax =254 nm; HRMS (EI): m/z: calcd for
C29H22Cl2O4: 504.0895; found: 504.0883.
[10] a) B. L. Merner, L. N. Dawe, G. J. Bodwell, Angew. Chem. 2009, 121,
5595–5599; Angew. Chem. Int. Ed. 2009, 48, 5487–5491; b) U. J.
Lorenz, N. Solcà, J. Lemaire, P. Maître, O. Dopfer, Angew. Chem.
2007, 119, 6834–6837; Angew. Chem. Int. Ed. 2007, 46, 6714–6716.
[11] N. H. Sherden, D. C. Behenna, S. C. Virgil, B. M. Stoltz, Angew.
Chem. 2009, 121, 6972–6975; Angew. Chem. Int. Ed. 2009, 48, 6840–
6843.
Acknowledgements
We are grateful to the National Science Foundation of China (20872002,
20572001) for financial support. We also thank Dr. Qinghai Li and Prof.
Xiaolong Mu for X-ray crystallography.
[12] Crystal data for 3ab: C35H30O4; MW =514.59; triclinic; space group
¯
P1; final R indices [I>2s(I)], R1=0.0766, wR2=0.2149; R indices
(all data): R1=0.0890, wR2=0.2303; a=11.075(4) ꢁ, b=
11.162(4) ꢁ, c=13.153(8) ꢁ; b=100.108(6)8; V=1736.7(11) ꢁ3; T=
293(2) K, wavelength: 0.71073 ꢁ; Z=4; reflections collected/unique:
10590/5335 (Rint =0.080); number of observations [I>2s(I)] 4291,
parameters: 344.
[1] a) F. G. Brunetti, X. Gong, M. Tong, A. J. Heeger, F. Wudl, Angew.
Chem. 2010, 122, 542–536; Angew. Chem. Int. Ed. 2010, 49, 532–
536; b) D. F. Perepichka, F. Rose, Science 2009, 323, 216–217.
[2] V. A. Dediu, L. E. Hueso, I. Bergenti, C. Taliani, Nat. Mater. 2009,
8, 707–716.
[3] a) A. Rajca, S. Rajca, Angew. Chem. 2010, 122, 683–685; Angew.
Chem. Int. Ed. 2010, 49, 672–674; b) I. Gupta, A. Srinivasan, T.
Morimoto, M. Toganoh, H. Furuta, Angew. Chem. 2008, 120, 4639–
4643; Angew. Chem. Int. Ed. 2008, 47, 4563–4567.
[13] a) D. Garcꢈa-Cuadrado, P. D. Mendoza, A. A. C. Braga, F. Maseras,
A. M. Echavarren, J. Am. Chem. Soc. 2007, 129, 6880–6886; b) D.
Garcia-Cuadrado, A. A. C. Braga, F. Maseras, A. M. Echavarren, J.
Am. Chem. Soc. 2006, 128, 1066–1067.
[14] SAINT and SADABS software Reference Manual, Bruker AXS
Inc., Madison, Wisconsin (USA), 2003.
7640
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ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2010, 16, 7635 – 7641

Fused Polyaromatic Hydrocarbon Construction
FULL PAPER
[15] a) SHELXL97, Program for Crystal Structure Refinement, G. M.
Sheldrick, University of Gçttingen, Gçttingen (Germany), 1997;
b) SHELXS97, Program for Crystal Structure Refinement, G. M.
Sheldrick, University of Gçttingen, Gçttingen (Germany), 1997;
c) G. M. Sheldrick, Acta Crystallogr. Sect. A 1990, 46, 467–473.
[16] G. A. Molander, E. P. Cormier, J. Org. Chem. 2005, 70, 2622–2626.
Received: March 17, 2010
Published online: May 21, 2010
Chem. Eur. J. 2010, 16, 7635 – 7641
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
7641