Synthesis of polyoxygenated dibenzo[a,e]cycloheptatrienes

Article abstract of DOI:10.1016/j.tet.2017.02.054

A successive route for the synthesis of substituted dibenzo[a,e]cycloheptatriene 1 was established by the reduction of 2-allylbenzaldehyde 4, the BF₃·OEt₂-mediated intermolecular coupling of 2-allylphenylmethanol 5 with oxygenated be

Full text of DOI:10.1016/j.tet.2017.02.054

Accepted Manuscript
Synthesis of polyoxygenated dibenzo[a,e]cycloheptatrienes
Chieh-Kai Chan, Yi-Ling Chan, Yu-Lin Tsai, Meng-Yang Chang
PII:
S0040-4020(17)30202-8
10.1016/j.tet.2017.02.054
TET 28495
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 23 January 2017
Revised Date: 22 February 2017
Accepted Date: 24 February 2017
Please cite this article as: Chan C-K, Chan Y-L, Tsai Y-L, Chang M-Y, Synthesis of polyoxygenated
dibenzo[a,e]cycloheptatrienes, Tetrahedron (2017), doi: 10.1016/j.tet.2017.02.054.
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Synthesis of Polyoxygenated Dibenzo[a,e]cycloheptatrienes
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Chieh-Kai Chan, Yi-Ling Chan, Yu-Lin Tsai and Meng-Yang Chang
Department of Medicinal and Applied Chemistry, Kaohsiung Medical University Hospital, Kaohsiung Medical University, Kaohsiung 807, Taiwan

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Tetrahedron
journal homepage: www.elsevier.com
Synthesis of Polyoxygenated Dibenzo[a,e]cycloheptatrienes
Chieh-Kai Chan, Yi-Ling Chan, Yu-Lin Tsai and Meng-Yang Chang
Department of Medicinal and Applied Chemistry, Kaohsiung Medical University Hospital, Kaohsiung Medical University, Kaohsiung 807, Taiwan
ARTICLE INFO
ABSTRACT
Article history:
Received
A successive route for the synthesis of substituted dibenzo[a,e]cycloheptatriene 1 was
established by the reduction of 2-allylbenzaldehyde 4, the BF3 OEt2-mediated intermolecular
.
Received in revised form
Accepted
Available online
coupling of 2-allylphenylmethanol 5 with oxygenated benzenes 6, the olefinic oxidative
cleavage of 7 and the intramolecular ring-closure of 8. Functionalized anthracene 13 were
prepared from 2-vinylbenzaldehyde 9. The key structures were confirmed by X-ray single
crystal diffraction analysis.
Keywords:
dibenzo[a,e]cycloheptatrienes,
anthracenes,
2-allylbenzaldehyde,
medium ring,
Friedel-Crafts,
annulation
———
Corresponding author. Tel.: +866-7-312-1101x2220; e-mail: mychang@cc.kmu.edu.tw.

2
Tetrahedron
ACCEPTED MANUSCRIPT
1. Introduction
Medium-sized carbocyclic rings fused with mono- or
dibenzoannulated scaffolds are crucial frameworks in many
bioactive compounds, natural products, and chiral ligands and
represent some versatile intermediates in organic synthesis.[1]
Among these compounds, seven-membered dibenzo ring systems
are key structural motifs that have appeared in medicinal industry
and bioactive natural products with related properties and diverse
pharmaceutical activities.[2] As shown in Figure 1,
dibenzo[a,e]cycloheptatriene 1 possesses a characteristic tricyclic
core scaffold consisting of a doubly benzoannulated cycloheptene
ring. The carbocyclic core of 1 with two benzene rings adjacent
to a cycloheptene carbocycle has been observed in a number of
bioactive molecules and natural products.[3,4] Amurensinine (2a)
exhibits CNS activity for the treatment of Parkinson’s and
Alzheimer’s diseases,[4a-b] eberconazole (WS-2160, 2b) has been
developed as an antifungal agent,[4c-d] and rubialatin (2c) shows
cytotoxicity and a synergistic effect with TNF-α for NF-κB
activation.[4e] Diptoindonesin D (2d), a resveratrol-based natural
product, has potent antifungal activity and is cytotoxic against P-
388 murine leukemia cells.[4f-g] Compound 2e possesses an
acetamide chain resulting in a higher MT2 antagonist activity.[4h]
Scheme 2. Synthetic Route of Dibenzo[a,e]cycloheptatriene.
Scheme 3. Synthesis of 5.
Table 1. Synthesis of 7.a
Several strategies for the preparation of benzoannulated
seven-membered rings have been disclosed. These methods
include ring expansion reactions,[5] ring-closing metathesis,[6]
intermolecular cyclization,[7] intramolecular cycloadditions,[8] ene
reactions,[9] transition metal-mediated hydroacylation,[10] aryne
insertion into 1,3-dicarbonyls[11] and Friedel-Crafts reactions.[12]
The goal of this research is the development of a facile synthetic
entry
5
R1, R2, R3, R4 6 (OR)n
5a OMe, H, H, H 6a 1,2-(OMe)2
7 (%)b
7a, 92
1
2
5a OMe, H, H, H 6b 1,2,3-(OMe)3 7b, 90
3
5a
OMe, H, H, H 6c 1,2-CH2O2
7c, 95
7d, 94
4
5b OiPr, H, H, H 6a 1,2-(OMe)2
route
for
the
synthesis
of
polyoxygenated
substituted 2-
5
5b OiPr, H, H, H 6b 1,2,3-(OMe)3 7e, 88
dibenzo[a,e]cycloheptatrienes
from
6
5b OiPr, H, H, H 6c 1,2-CH2O2
5c OnBu, H, H, H 6a 1,2-(OMe)2
7f, 96
7g, 95
allylbenzaldehydes.
7
8
5c OnBu, H, H, H 6b 1,2,3-(OMe)3 7h, 87
9
5c OnBu, H, H, H 6c 1,2-CH2O2
5d OC5H9, H, H, H6a 1,2-(OMe)2
7i, 93
7j, 95
10
11
12
13
14
15
16
17
18
19
20
5d OC5H9, H, H, H6b 1,2,3-(OMe)3 7k, 86
5d OC5H9, H, H, H6c 1,2-CH2O2
5e OMe, Me, H, H 6a 1,2-(OMe)2
7l, 93
7m, 96
5e OMe, Me, H, H 6b 1,2,3-(OMe)3 7n, 90
5e OMe, Me, H, H 6c 1,2-CH2O2
5f H, H, OMe, Me 6a 1,2-(OMe)2
7o, 94
7p, 95
Figure 1. Selected Dibenzo Seven-membered Ring Structures.
5f H, H, OMe, Me 6b 1,2,3-(OMe)3 7q, 92
5a OMe, H, H, H 6d 1,2-(OiPr)2
7r, 94
2. Results and discussions
5a OMe, H, H, H 6e 1-OMe-2-OiPr 7s/7t, 94
5a OMe, H, H, H 6f 1-OBn-2-OMe 7u/7v, 92
Recently, we became interested in the development of
synthetic routes toward benzofused bicyclic skeletons derived
from the commercially available isovanillin 3.[13] All of these
works were from versatile 2-allylbenzaldehydes 4, which were
easily prepared in high yield via a three-step procedure including
O-allylation, Claisen-type rearrangement and O-alkylation
(Scheme 1). Herein, we describe the synthetic route for the
synthesis of oxygenated dibenzo[a,e]cycloheptatriene from 2-
allylbenzaldehyde and veratrol via BF3.OEt2-mediated
intermolecular coupling and intramolecular ring-closure mono-
couple in a formal [5+2] annulation, as shown in Scheme 2.
a Coupling conditions: 5 (1.0 mmol), 6 (1.3 mmol), BF3.OEt2 (0.5 mmol),
CH2Cl2 (8 mL), 25 oC, 2 h.
b Isolated yields.
Initially, we used the developed method to create skeleton 7
from a two-step synthetic route including (i) the reduction of
benzaldehyde 4 by NaBH4, and (ii) the BF3.OEt2-mediated
intermolecular coupling with oxygenated benzene 6.[14] As shown
in Scheme 3 and Table 1, the NaBH4-mediated reduction of
aldehyde 4 gave 2-allylphenylmethanol 5 in high yields (95%).
.
We believed that BF3 OEt2/CH2Cl2 conditions were appropriate to
conduct the intermolecular coupling of 5 with 6. In entry 1, the
reaction of 5a (R1 = OMe, R2 = R3 = R4 = H) and veratrol (6a)
was employed to afford 7a in 92% yield. Other oxygenated
benzenes of 6, such as 1,2,3-trimethoxybenzene (6b) and 1,3-
benzodioxole (6c), were also suitable for the formation of 7b and
Scheme 1. Three-step synthesis of 4.

7c (entries 2-3). Changing the R1 substituent on 5, 5b (R1 = OiPr),
ACCEPTED MANUSCRIPT
5c (R1 = OnBu), and 5d (R1 = OC5H9) were reacted with 6a-d to
afford 7d-l in yields ranging from 86% to 96% (entries 4-12). In
addition, the reaction of 5e (R1 = OMe, R2 = Me, R3 = R4 = H)
with 6a-c, and 5f (R1 = R2 = H, R3 = OMe, R4 = Me) with 6a-b,
provided 7m-q in excellent yields (90-96%, entries 13-17).
Sterically hindered, 1,2-diisopropoxybenzene 6d treated with 5a
gave the desired 7r in 94% yield (entry 18). The treatment of
unsymmetrical 1-isopropoxy-2-methoxybenzene (6e) with 5a
gave a mixture of 7s and 7t in a ratio of 2:1 and a 94% yield.
1a, 88%
1b, 89%
1c, 90%
O
Likewise, 1-benzyloxy-2-methoxybenzene (6f) with 5a,
a
MeO
mixture of 7u and 7v in a ratio of 1:1 with a 90% yield (entries
19-20). From the electronic effect point of view, the electron-
donating oxygenated (RO) group could provide more electron
density for aryl system such that coupling reactions were well-
performed. Attempts to the BF3.OEt2-mediated intermolecular
coupling of 5a and benzene failed to isolate the desired product
due to no involvement of electron-donating groups. Changing
from electron-donating oxygenated groups (veratrol) to electron-
donating nitrogenated groups (N,N-dimethylaniline), attempts to
apply other electron-rich nitrogenated benzenes failed to afford
desired product in the coupling reaction of 5. For electron-
withdrawing aryls, methyl benzoate and nitrobenzene were
examined in the intermolecular coupling reaction of 5. No
corresponding product was isolated. However, the substrate
scope is limited for the synthetic routes.
OMe
OMe
MeO
1d, 92%
1g, 91%
1e, 87%
1f, 90%
1i, 90%
1h, 86%
1j, 92%
1k, 84%
1n, 82%
1l, 85%
1o, 88%
1m, 91%
On the basis of our experience in using a one-pot combination
of OsO4/NaIO4 in the synthesis of functionalized
isoquinolines,[13c] benzo[g]indazoles,[13d] and 3-benzazepines,[13e]
we believed that it was possible to transform benzyl 7 to
aldehyde
8 without purification of any intermediates. A
1p, 95%
1q, 91%
1r, 95%
successive BF3.OEt2-mediated intramolecular Friedel-Crafts type
reaction was then used for the synthesis of substituted
dibenzo[a,e]cycloheptatrienes. As expected, this one-pot
preparation of 1 from 7 proceeded smoothly via a two-step
1s + 1t, 93% (2 : 1)
1u, 44% + 1v, 44%
procedure involving (i) an OsO4/NaIO4-mediated oxidative
cleavage of the olefin and (ii)
.
a
BF3 OEt2-faciliated
intramolecular Friedel-Crafts type cyclization. Substrates with
substitution at the R1 position, 7a-l (R1 = OMe, OiPr, OnBu and
OC5H9), afforded 1a-l in 84-92% yields. Substituents at R2 or R3
on 7m-q did not affect the results of the two-step procedure and
afforded 1m (R2 = Me, R3 = H) and 1q (R2 = H, R3 = OMe) with
82% and 95% yields, respectively. Again, no lowering of yield
was observed in the formation of sterically hindered 1r.
Unsymmetrical substrates 7s and 7t were utilized as an
inseparable mixture, affording 1s and 1t in a ratio of 2:1, with a
93% yield. Although the isomers 1u and 1v were separated from
a starting mixture of 7u and 7v, no significant regiocontrol was
observed. All product structures and corresponding yields are
shown in Table 2.
a Conditions: (i) 7 (0.6 mmol), OsO4 (2.5% in THF, 0.6 mL), NMO (50% in
H2O, 1.3 mmol), THF/H2O (v/v = 1/1, 12 mL), 25 oC, 2 h; then NaIO4 (0.7
mmol), 25 oC, 1 h, (ii) BF3.OEt2 (0.5 mmol), CH2Cl2 (8 mL), 25 oC, 2 h.
b Isolated yields.
The structures of 1l and 1p were determined by single-crystal
X-ray crystallography.[15] For crystal structures of 1l and 1p, we
observed that 1l belonged to triclinic crystal system with P -1
space group, and 1p was orthorhombic crystal system with P n m
a space group (see Table 3). Single-crystal X-ray diffraction
analysis was employed to prove the constitution and relative
configuration of dibenzo[a,e]cycloheptatriene. Two ORTEP plots
clearly showed that the tricyclic ring system possessed a bowl-
like configuration. (see Supporting Information). We
hypothesized that the migration of the olefin group of 4 to an
interna position might allow a intramolecular ring-closure mono-
couple formal [4+2] annulation for the preparation of anthracene
(Scheme 4).
Table 2. Synthesis of 1.a,b
Table 3. Crystal Data for 1l and 1p

4
Tetrahedron
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CCDC number
1446967 (1l)
1450478 (1p)
Crystal system
Space group
a (Å)
b (Å)
c (Å)
triclinic
P -1
orthorhombic
P n m a
10.2063(6)
26.4494(15)
6.0198(4)
90
9.4510(6)
9.7866(6)
11.0042(7)
105.463(3)
102.774(3)
105.821(3)
895.19(10) / 2
296(2)
α (°)
β (°)
γ (°)
90
90
Volume (Å3) / Z
Temperature (K)
1625.05(17) / 4
296(2)
Dc (Mg/m3)
1.300
1.277
Absorption
0.089
0.089
coefficient (mm-1)
Crystal size (mm)
θ range for data
collection (°)
0.20 x 0.20 x 0.18
2.024 to 26.378
15138
0.25 x 0.20 x 0.18
1.540 to 26.478
12086
Reflections collected
Independent
3645(Rint=0.0321)
1712(Rint=0.0348)
reflections
RF, Rw(F2) (all data)a
0.0600, 0.1408
0.0438, 0.1279
1.074
0.055, 0.1102
0.0406, 0.1005
1.050
RF, Rw(F2) (I > 2σ(I))a
GOF
W
W
a RF =Σ|Fo-Fc|/Σ|Fo|; RW (F2) = [Σ |Fo -Fc2|2/Σ Fo ]
2
4 1/2
As shown in Scheme 5, NaOH in MeOH was used to
transform the terminal double bond to an internal double
bond.[13a-b,16] Compounds 9a-c were isolated as the sole (E)-
isomer form in 91-93% yields. The reduction of aldehyde 9a-c by
NaBH4 gave 10a-c in high yields. As in the above results in
Table 1, the intermolecular coupling with oxygenated benzene 6
(1.0 equiv) afforded 11a-e in 85-90% yield. Based on the results
shown in Table 2, the oxidative cleavage of the internal olefin
Scheme 6. Synthesis of 14a-l.
According to our experience in the synthesis of
polyoxygenated dibenzo[a,e]cycloheptatriene 1 and anthracene
13, oxygenated benzene 6 plays important roles in intermolecular
and intramolecular Friedel-Crafts type reactions. Therefore, we
further explored the reaction of excess phenylmethanol 5 with
.
with the OsO4/NaIO4 system, followed by BF3 OEt2-mediated
intramolecular Friedel-Crafts type reaction and aromatization,
gave anthracenes 13a-e in good to excellent yields. The structure
oxygenated benzene
6 (0.6 equiv). In cases where two
oxygenated substituents were present on 6, such as 6a and 6c-f,
we changed the equivalents of 6 from 1.3 to 0.6. As shown in
Scheme 6, the double intermolecular couplings showed complete
conversion under the BF3.OEt2/CH2Cl2 condition, and the 14a-l
were isolated in good to excellent yields (83-95%). Disubstituted
alkene 10a was also suitable for the double coupling with 6a (0.6
equiv), giving 14m in 88% yield. Using the m-dimethoxy 6g (0.6
equiv) in the double coupling with 5a and 5e gave 14n and 14o,
respectively, in high yields (Scheme 7). However, attempts to
afford [6,7,6,7,6]-pentacyclic 15 from 14a was unsuccessful due
to poor nucleophilicity on the ortho position of methoxy
substituent under the optimized conditions (Scheme 8).
of
13a
was
determined
by
single-crystal
X-ray
crystallography.[15]
Scheme 4. Synthetic Route of Anthracene.
Scheme 7. Synthesis of 14m-o.
Scheme 5. Synthesis of 13.

4.2.2. 2-Allyl-3-isopropoxy-4-methoxyphenylmethanol (5b).
ACCEPTED MANUSCRIPT
According to the general procedure, the reaction was performed
in the presence of NaBH4 (76 mg, 2.0 mmol) and 4b (234 mg, 1.0
o
mmol) in a cosolvent of THF (5 mL) and MeOH (5 mL) at 0 C
for 0.5 h. Purification on silica gel (hexanes/EtOAc = 4/1)
afforded 5b (95%, 224 mg). Colorless gum; HRMS (ESI,
Scheme 8. Reaction of 14a.
1
M++Na) calcd for C14H20O3Na 259.1304, found 259.1312; H
NMR (400 MHz, CDCl3): δ 7.04 (d, J = 8.4 Hz, 1H), 6.77 (d, J =
8.4 Hz, 1H), 6.01-5.91 (m, 1H), 4.98 (dq, J = 1.6, 10.4 Hz, 1H),
4.92 (dq, J = 1.6, 17.2 Hz, 1H), 4.57 (s, 2H), 4.53-4.47 (m, 1H),
3.81 (s, 3H), 3.54 (dt, J = 1.6, 6.0 Hz, 2H), 2.01 (br s, 1H), 1.26
(d, J = 6.4 Hz, 6H); 13C NMR (100 MHz, CDCl3): δ 152.4, 144.9,
137.6, 132.3, 132.1, 123.7, 114.9, 109.9, 74.5, 63.0, 55.5, 30.5,
22.5 (2x).
3. Conclusion
In summary, we have developed a facile formal [5+2]
annulation for the synthesis of polyoxygenated
dibenzo[a,e]cycloheptatrienes from 2-allylbenzaldehydes. The
synthetic route includes an aldehyde reduction, intermolecular
coupling, oxidative olefin cleavage, and an intramolecular
Friedel-Crafts reaction and affords the desired products in good
to excellent yields. Additionally, a formal [4+2] annulation route
toward anthracene 13 was also established. When the amount of
oxygenated benzenes 6 was decreased, the corresponding 14 was
obtained in modest to good yield. The structures of some
products were confirmed by X-ray crystallography.
4.2.3.
2-Allyl-3-butoxy-4-methoxyphenylmethanol
(5c).
According to the general procedure, the reaction was performed
in the presence of NaBH4 (76 mg, 2.0 mmol) and 4c (248 mg, 1.0
o
mmol) in a cosolvent of THF (5 mL) and MeOH (5 mL) at 0 C
for 0.5 h. Purification on silica gel (hexanes/EtOAc = 5/1)
afforded 5c (95%, 238 mg). Colorless solid; mp = 37-38 oC
(recrystallized from hexanes and EtOAc); HRMS (ESI, M++Na)
4. Experimental section
4.1. General
1
calcd for C15H22O3Na 273.1460, found 273.1462; H NMR (400
MHz, CDCl3): δ 7.02 (d, J = 8.4 Hz, 1H), 6.74 (d, J = 8.4 Hz,
1H), 6.02-5.92 (m, 1H), 4.97 (dq, J = 1.6, 10.4 Hz, 1H), 4.90 (dq,
J = 1.6, 17.2 Hz, 1H), 4.53 (s, 2H), 3.91 (t, J = 6.8 Hz, 2H), 3.80
(s, 3H), 3.50 (d, J = 6.0 Hz, 2H), 2.42 (br s, 1H), 1.78-1.71 (m,
2H), 1.54-1.44 (m, 2H), 0.96 (t, J = 7.2 Hz, 3H); 13C NMR (100
MHz, CDCl3): δ 152.2, 146.4, 137.5, 132.1, 131.6, 123.9, 114.7,
109.9, 72.8, 62.6, 55.4, 32.2, 30.0, 19.0, 13.7.
All other reagents and solvents were obtained from
commercial sources and used without further purification.
Reactions were routinely carried out under an atmosphere of dry
nitrogen with magnetic stirring. Products in organic solvents
were dried with anhydrous magnesium sulfate before
concentration in vacuo. Melting points were determined with a
1
melting apparatus. H and 13C NMR spectra were recorded on a
4.2.4. 2-Allyl-3-(cyclopentyloxy)-4-methoxyphenylmethanol
(5d). According to the general procedure, the reaction was
performed in the presence of NaBH4 (76 mg, 2.0 mmol) and 4d
(260 mg, 1.0 mmol) in a cosolvent of THF (5 mL) and MeOH (5
mL) at 0 oC for 0.5 h. Purification on silica gel (hexanes/EtOAc =
5/1) afforded 5d (95%, 249 mg). Colorless gum; HRMS (ESI,
spectrometer operating at 400 and at 100 MHz, respectively.
Chemical shifts (δ) are reported in parts per million (ppm) and
the coupling constants (J) are given in Hertz. High resolution
mass spectra (HRMS) were measured with a mass spectrometer
microTOF-Q by ESI using a hybrid ion-trap. X-ray crystal
structures were obtained with a diffractometer (CAD4, Kappa
CCD).
1
M++Na) calcd for C16H22O3Na 285.1460, found 285.1463; H
NMR (400 MHz, CDCl3): δ 7.03 (d, J = 8.4 Hz, 1H), 6.76 (d, J =
8.4 Hz, 1H), 6.00-5.90 (m, 1H), 4.97 (dq, J = 1.6, 10.4 Hz, 1H),
4.91 (dq, J = 1.6, 17.2 Hz, 1H), 4.86-4.82 (m, 1H), 4.56 (s, 2H),
3.81 (s, 3H), 3.50 (dt, J = 1.6, 6.0 Hz, 2H), 2.12 (br s, 1H), 1.89-
1.85 (m, 4H), 1.84-1.77 (m, 2H), 1.59-1.54 (m, 2H); 13C NMR
(100 MHz, CDCl3): δ 152.1, 145.3, 137.4, 132.3, 131.9, 123.5,
114.8, 110.1, 84.3, 62.9, 55.5, 32.7 (2x), 30.3, 23.6 (2x).
4.2. A representative synthetic procedure of skeleton 5 and 10
is as follows:
NaBH4 (76 mg, 2.0 mmol) was added to a solution of 4a-f or
9a-c (1.0 mmol) in a cosolvent of THF (5 mL) and MeOH (5
o
o
mL) at 0 C. The reaction mixture was stirred for 0.5 h at 0 C
and the solvent was concentrated. The residue was diluted with
water (10 mL) and the mixture was extracted with CH2Cl2 (3 x 20
mL). The combined organic layers were washed with brine,
dried, filtered and evaporated to afford crude product.
Purification on silica gel (hexanes/EtOAc = 5/1~3/1) afforded
skeletons 5 and 10.
4.2.5. 2-(But-3-en-2-yl)-3,4-dimethoxyphenylmethanol (5e).
According to the general procedure, the reaction was performed
in the presence of NaBH4 (76 mg, 2.0 mmol) and 4e (220 mg, 1.0
o
mmol) in a cosolvent of THF (5 mL) and MeOH (5 mL) at 0 C
for 0.5 h. Purification on silica gel (hexanes/EtOAc = 4/1)
afforded 5e (95%, 211 mg). Colorless gum; HRMS (ESI,
4.2.1. 2-Allyl-3,4-dimethoxyphenylmethanol (5a). According
to the general procedure, the reaction was performed in the
presence of NaBH4 (76 mg, 2.0 mmol) and 4a (206 mg, 1.0
mmol) in a cosolvent of THF (5 mL) and MeOH (5 mL) at 0 C
for 0.5 h. Purification on silica gel (hexanes/EtOAc = 4/1)
1
M++Na) calcd for C13H18O3Na 245.1148, found 245.1150; H
NMR (400 MHz, CDCl3): δ 7.03 (d, J = 8.4 Hz, 1H), 6.76 (d, J =
8.4 Hz, 1H), 6.26-6.17 (m, 1H), 5.04 (dt, J = 1.6, 8.8 Hz, 1H),
5.01 (q, J = 1.6 Hz, 1H), 4.62 (d, J = 12.4 Hz, 1H), 4.58 (d, J =
12.4 Hz, 1H), 4.04-3.97 (m, 1H), 3.83 (s, 3H), 3.80 (s, 3H), 2.08
(br s, 1H), 1.43 (d, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): δ 152.7, 147.6, 143.2, 137.8, 131.5, 124.9, 112.8, 110.0,
63.2, 60.5, 55.5, 36.3, 19.3.
o
afforded 5a (95%, 198 mg). Colorless gum; HRMS (ESI,
1
M++Na) calcd for C12H16O3Na 231.0992, found 231.0993; H
NMR (400 MHz, CDCl3): δ 7.07 (d, J = 8.4 Hz, 1H), 6.79 (d, J =
8.4 Hz, 1H), 6.06-5.96 (m, 1H), 5.01 (dq, J = 1.6, 10.0 Hz, 1H),
4.92 (dq, J = 1.6, 17.2 Hz, 1H), 4.58 (s, 2H), 3.85 (s, 3H), 3.80 (s,
3H), 3.52 (dt, J = 1.6, 5.6 Hz, 2H), 1.84 (br s, 1H); 13C NMR
(100 MHz, CDCl3): δ 152.4, 147.3, 137.7, 132.1, 131.8, 124.4,
115.0, 110.1, 63.0, 60.7, 55.6, 30.0.
4.2.6. 2-(But-2-en-1-yl)-4,5-dimethoxyphenylmethanol (5f).
According to the general procedure, the reaction was performed
in the presence of NaBH4 (76 mg, 2.0 mmol) and 4f (220 mg, 1.0
o
mmol) in a cosolvent of THF (5 mL) and MeOH (5 mL) at 0 C
for 0.5 h. Purification on silica gel (hexanes/EtOAc = 3/1)

6
Tetrahedron
afforded 5f (95%, 211 mg). Colorless gum; HRMS (ESI,
(208 mg, 1.0 mmol) and 6a (180 mg, 1.3 mmol) in CH Cl (8
ACCEPTED MANUSCRIPT
2 2
M++Na) calcd for C13H18O3Na 245.1148, found 245.1150; H
NMR (400 MHz, CDCl3): δ 6.89 (s, 1H), 6.66 (s, 1H), 5.58-5.51
(m, 1H), 5.44-5.35 (m, 1H), 4.57 (s, 2H), 3.83 (s, 3H), 3.81 (s,
3H), 3.28 (d, J = 6.0 Hz, 2H), 1.63 (dd, J = 1.2, 6.0 Hz, 3H), 2.21
(br s, 1H); 13C NMR (100 MHz, CDCl3): δ 148.1, 147.1, 130.8
(2x), 130.7, 130.1, 126.0, 112.9, 111.8, 62.4, 55.8, 35.1, 17.7.
mL) at 25 oC for 2 h. Purification on silica gel (hexanes/EtOAc =
1
4/1) afforded 7a (92%, 302 mg). Colorless gum; HRMS (ESI,
M++Na) calcd for C20H24O4Na 351.1565, found 351.1568; H
1
NMR (400 MHz, CDCl3): δ 6.79-6.73 (m, 3H), 6.66-6.61 (m,
2H), 5.97-5.87 (m, 1H), 5.00 (dq, J = 1.6, 10.0 Hz, 1H), 4.92 (dq,
J = 1.6, 17.2 Hz, 1H), 3.88 (s, 2H), 3.85 (s, 3H), 3.84 (s, 3H),
3.82 (s, 3H), 3.81 (s, 3H), 3.42 (dt, J = 1.6, 6.0 Hz, 2H); 13C
NMR (100 MHz, CDCl3): δ 151.2, 148.9, 147.5, 147.3, 136.9,
133.5, 132.5, 132.1, 125.3, 120.7, 114.9, 112.1, 111.1, 110.1,
60.8, 55.9, 55.8, 55.6, 37.7, 30.6.
4.2.7. 3,4-Dimethoxy-2-(prop-1-en-1-yl)phenylmethanol (10a).
According to the general procedure, the reaction was performed
in the presence of NaBH4 (76 mg, 2.0 mmol) and 9a (206 mg, 1.0
o
mmol) in a cosolvent of THF (5 mL) and MeOH (5 mL) at 0 C
for 0.5 h. Purification on silica gel (hexanes/EtOAc = 4/1)
4.3.2.
2-Allyl-3,4-dimethoxy-1-(2,3,4-
afforded 10a (95%, 198 mg). Colorless gum; HRMS (ESI,
trimethoxybenzyl)benzene (7b). According to the general
procedure, the reaction was performed in the presence of
BF3·OEt2 (71 mg, 0.5 mmol), 5a (208 mg, 1.0 mmol) and 6b
(219 mg, 1.3 mmol) in CH2Cl2 (8 mL) at 25 oC for 2 h.
Purification on silica gel (hexanes/EtOAc = 4/1) afforded 7b
(90%, 323 mg). Colorless gum; HRMS (ESI, M++Na) calcd for
C21H26O5Na 381.1670, found 381.1671; 1H NMR (400 MHz,
CDCl3): δ 6.72 (d, J = 8.8, 10.0 Hz, 2H), 6.62-6.55 (m, 2H),
5.99-5.89 (m, 1H), 4.99 (dq, J = 1.6, 10.0 Hz, 1H), 4.94 (dq, J =
1.6, 16.8 Hz, 1H), 3.88 (s, 3H), 3.86 (s, 2H), 3.82 (s, 3H), 3.81 (s,
6H), 3.78 (s, 3H), 3.46 (dt, J = 1.6, 6.0 Hz, 2H); 13C NMR (100
MHz, CDCl3): δ 152.0, 151.6, 150.8, 147.2, 142.1, 136.7, 132.2,
131.9, 126.8, 124.8, 124.0, 114.6, 109.9, 106.9, 60.6, 60.5, 60.4,
55.7, 55.4, 31.6, 30.4.
1
M++Na) calcd for C12H16O3Na 231.0992, found 231.0995; H
NMR (400 MHz, CDCl3): δ 7.08 (d, J = 8.4 Hz, 1H), 6.76 (d, J =
8.4 Hz, 1H), 6.50 (dd, J = 1.6, 16.0 Hz, 1H), 6.24-6.15 (m, 1H),
4.60 (s, 2H), 3.84 (s, 3H), 3.73 (s, 3H), 1.96 (br s, 1H), 1.92 (dd,
J = 1.6, 6.4 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 152.3,
146.8, 132.1, 131.7, 131.4, 124.5, 123.6, 110.2, 63.3, 60.0, 55.7,
19.4.
4.2.8.
3-Isopropoxy-4-methoxy-2-(prop-1-en-1-
yl)phenylmethanol (10b). According to the general procedure,
the reaction was performed in the presence of NaBH4 (76 mg, 2.0
mmol) and 9b (234 mg, 1.0 mmol) in a cosolvent of THF (5 mL)
o
and MeOH (5 mL) at 0 C for 0.5 h. Purification on silica gel
(hexanes/EtOAc = 4/1) afforded 10b (95%, 224 mg). Colorless
gum; HRMS (ESI, M++Na) calcd for C14H20O3Na 259.1304,
4.3.3.
5-(2-Allyl-3,4-dimethoxybenzyl)benzo[d][1,3]dioxole
1
found 259.1306; H NMR (400 MHz, CDCl3): δ 7.06 (d, J = 8.4
(7c). According to the general procedure, the reaction was
performed in the presence of BF3·OEt2 (71 mg, 0.5 mmol), 5a
(208 mg, 1.0 mmol) and 6c (159 mg, 1.3 mmol) in CH2Cl2 (8
mL) at 25 oC for 2 h. Purification on silica gel (hexanes/EtOAc =
4/1) afforded 7c (95%, 297 mg). Colorless gum; HRMS (ESI,
Hz, 1H), 6.75 (d, J = 8.4 Hz, 1H), 6.49 (dq, J = 1.6, 16.0 Hz, 1H),
6.14 (dq, J = 6.4, 16.0 Hz, 1H), 4.60 (s, 2H), 4.36-4.30 (m, 1H),
3.81 (s, 3H), 1.91-1.89 (m, 4H), 1.23 (d, J = 6.4 Hz, 6H); 13C
NMR (100 MHz, CDCl3): δ 152.6, 144.8, 132.7, 131.9, 131.3,
124.6, 124.0, 110.1, 75.1, 63.5, 55.6, 22.4 (2x), 19.2.
1
M++Na) calcd for C19H20O4Na 335.1253, found 335.1255; H
NMR (400 MHz, CDCl3): δ 6.80 (d, J = 8.4 Hz, 1H), 6.76 (d, J =
8.4 Hz, 1H), 6.73 (d, J = 8.4 Hz, 1H), 6.59 (s, 1H), 6.58 (d, J =
8.4 Hz, 1H), 5.97-5.87 (m, 1H), 5.91 (s, 2H), 5.00 (dq, J = 1.6,
10.0 Hz, 1H), 4.92 (dq, J = 1.6, 17.2 Hz, 1H), 3.86 (s, 2H), 3.85
(s, 3H), 3.82 (s, 3H), 3.40 (dt, J = 2.4, 6.0 Hz, 2H); 13C NMR
(100 MHz, CDCl3): δ 151.2, 147.6, 147.5, 145.7, 145.6, 136.8,
134.9, 132.3, 125.4, 121.5, 114.8, 110.2, 109.2, 108.0, 100.7,
60.8, 55.6, 37.8, 30.5.
4.2.9. 3-Butoxy-4-methoxy-2-(prop-1-en-1-yl)phenylmethanol
(10c). According to the general procedure, the reaction was
performed in the presence of NaBH4 (76 mg, 2.0 mmol) and 9c
(248 mg, 1.0 mmol) in a cosolvent of THF (5 mL) and MeOH (5
mL) at 0 oC for 0.5 h. Purification on silica gel (hexanes/EtOAc =
4/1) afforded 10c (95%, 238 mg). Colorless gum; HRMS (ESI,
M++Na) calcd for C15H22O3Na 273.1460, found 273.1462; 1H
NMR (400 MHz, CDCl3): δ 7.05 (d, J = 8.4 Hz, 1H), 6.75 (d, J =
8.4 Hz, 1H), 6.48 (dq, J = 1.6, 16.0 Hz, 1H), 6.16 (dq, J = 6.4,
16.0 Hz, 1H), 4.59 (s, 2H), 3.84 (t, J = 5.6 Hz, 2H), 3.82 (s, 3H),
2.00 (br s, 1H), 1.91 (dd, J = 1.6, 6.4 Hz, 3H), 1.75-1.67 (m, 2H),
1.53-1.44 (m, 2H), 0.95 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): δ 152.4, 146.1, 132.01, 131.95, 131.3, 124.2, 123.8,
114.8, 110.2, 72.4, 63.3, 55.7, 32.2, 19.1, 13.8.
4.3.4.
2-Allyl-1-(3,4-dimethoxybenzyl)-3-isopropoxy-4-
methoxybenzene (7d). According to the general procedure, the
reaction was performed in the presence of BF3·OEt2 (71 mg, 0.5
mmol), 5b (236 mg, 1.0 mmol) and 6a (180 mg, 1.3 mmol) in
CH2Cl2 (8 mL) at 25 oC for 2 h. Purification on silica gel
(hexanes/EtOAc = 4/1) afforded 7d (94%, 335 mg). Colorless
gum; HRMS (ESI, M++Na) calcd for C22H28O4Na 379.1877,
4.3. A representative synthetic procedure of skeletons 7 and
11 is as follows:
1
found 379.1879; H NMR (400 MHz, CDCl3): δ 6.79-6.73 (m,
3H), 6.64-6.61 (m, 2H), 5.95-5.85 (m, 1H), 4.99 (dq, J = 1.6,
10.4 Hz, 1H), 4.93 (dq, J = 1.6, 17.2 Hz, 1H), 4.57-4.51 (m, 1H),
3.90 (s, 2H), 3.85 (s, 3H), 3.81 (s, 3H), 3.79 (s, 3H), 3.44 (dt, J =
1.6, 5.6 Hz, 2H), 1.27 (d, J = 6.0 Hz, 6H); 13C NMR (100 MHz,
CDCl3): δ 151.2, 148.7, 147.1, 145.0, 136.6, 133.6, 132.43,
132.35, 124.7, 120.5, 114.7, 111.9, 111.0, 109.9, 74.2, 55.7, 55.6,
55.4, 37.7, 30.9, 22.5 (2x).
BF3·OEt2 (71 mg, 0.5 mmol) was added to a solution of 5a-5f,
10a-10c (1.0 mmol) and 6a-f (1.3 mmol) in CH2Cl2 (8 mL) at 25
oC. The reaction mixture was stirred at 25 oC for 2 h. The
reaction mixture was concentrated and the residue was diluted
with water (10 mL) and the mixture was extracted with CH2Cl2
(3 x 20 mL). The combined organic layers were washed with
brine, dried, filtered and evaporated to afford crude product under
reduced pressure. Purification on silica gel (hexanes/EtOAc =
4/1) afforded 7a-7v and 11a-11e.
4.3.5.
2-Allyl-3-isopropoxy-4-methoxy-1-(2,3,4-
trimethoxybenzyl)benzene (7e). According to the general
procedure, reaction was performed in the presence of BF3·OEt2
(71 mg, 0.5 mmol), 5b (236 mg, 1.0 mmol) and 6b (219 mg, 1.3
4.3.1. 2-Allyl-1-(3,4-dimethoxybenzyl)-3,4-dimethoxybenzene
(7a). According to the general procedure, the reaction was
performed in the presence of BF3·OEt2 (71 mg, 0.5 mmol), 5a
o
mmol) in CH2Cl2 (8 mL) at 25 C for 2 h. Purification on silica

gel (hexanes/EtOAc = 4/1) afforded 7e (88%, 340 mg). Colorless
4.3.9.
5-(2-Allyl-3-butoxy-4-
ACCEPTED MANUSCRIPT
gum; HRMS (ESI, M++Na) calcd for C23H30O5Na 409.1982,
methoxybenzyl)benzo[d][1,3]dioxole (7i). According to the
general procedure, reaction was performed in the presence of
BF3·OEt2 (71 mg, 0.5 mmol), 5c (250 mg, 1.0 mmol) and 6c (159
mg, 1.3 mmol) in CH2Cl2 (8 mL) at 25 oC for 2 h. Purification on
silica gel (hexanes/EtOAc = 4/1) afforded 7i (93%, 330 mg).
Colorless gum; HRMS (ESI, M++Na) calcd for C22H26O4Na
1
found 409.1986; H NMR (400 MHz, CDCl3): δ 6.71 (d, J = 8.4
Hz, 1H), 6.67 (d, J = 8.4 Hz, 1H), 6.59 (d, J = 8.4 Hz, 1H), 6.56
(d, J = 8.4 Hz, 1H), 5.96-5.87 (m, 1H), 4.99 (dq, J = 1.6, 10.0 Hz,
1H), 4.93 (dq, J = 1.6, 17.2 Hz, 1H), 4.57-4.48 (m, 1H), 3.88 (s,
3H), 3.85 (s, 2H), 3.82 (s, 3H), 3.79 (s, 3H), 3.76 (s, 3H), 3.49 (dt,
J = 1.6, 6.0 Hz, 2H), 1.28 (d, J = 6.0 Hz, 6H); 13C NMR (100
MHz, CDCl3): δ 152.0, 151.0, 144.9, 142.2, 136.6, 132.4, 132.3,
127.1, 124.3, 124.0, 114.6, 109.9, 107.0, 105.1, 74.2, 60.6, 60.5,
55.8, 55.4, 31.8, 30.9, 22.5 (2x).
1
377.1721, found 377.1725; H NMR (400 MHz, CDCl3): δ 6.77
(d, J = 8.4 Hz, 1H), 6.75 (s, 1H), 6.72 (d, J = 8.4 Hz, 1H), 6.58 (s,
2H), 5.96-5.86 (m, 1H), 5.91 (s, 2H), 4.99 (dq, J = 1.6, 10.0 Hz,
1H), 4.91 (dq, J = 1.6, 17.2 Hz, 1H), 3.93 (t, J = 6.4 Hz, 2H),
3.85 (s, 2H), 3.83 (s, 3H), 3.40 (dt, J = 1.6, 6.0 Hz, 2H), 1.79-
1.72 (m, 2H), 1.55-1.47 (m, 2H), 0.97 (t, J = 7.2 Hz, 3H); 13C
NMR (100 MHz, CDCl3): δ 151.4, 147.6, 145.6, 136.9, 135.0,
132.3, 132.2, 125.2, 124.5, 121.5, 114.7, 110.1, 109.2, 108.0,
100.7, 72.9, 55.6, 37.8, 32.4, 30.6, 19.2, 13.9.
4.3.6.
5-(2-Allyl-3-isopropoxy-4-
methoxybenzyl)benzo[d][1,3]dioxole (7f).
According to the general procedure, reaction was performed in
the presence of BF3·OEt2 (71 mg, 0.5 mmol), 5b (236 mg, 1.0
mmol) and 6c (159 mg, 1.3 mmol) in CH2Cl2 (8 mL) at 25 oC for
2 h. Purification on silica gel (hexanes/EtOAc = 4/1) afforded 7f
(96%, 327 mg). Colorless gum; HRMS (ESI, M++Na) calcd for
C21H24O4Na 363.1565, found 363.1568; 1H NMR (400 MHz,
CDCl3): δ 6.76 (d, J = 8.4 Hz, 1H), 6.73 (d, J = 8.4 Hz, 1H), 6.72
(d, J = 7.6 Hz, 1H), 6.58 (s, 1H), 6.56-6.52 (m, 1H), 5.94-5.84 (m,
1H), 5.91 (s, 2H), 4.99 (dq, J = 1.6, 10.0 Hz, 1H), 4.92 (dq, J =
1.6, 17.2 Hz, 1H), 4.56-4.50 (m, 1H), 3.86 (s, 2H), 3.82 (s, 3H),
3.43 (dt, J = 1.6, 6.0 Hz, 2H), 1.28 (d, J = 6.0 Hz, 6H); 13C NMR
(100 MHz, CDCl3): δ 151.3, 147.6, 145.6, 145.2, 136.7, 135.1,
132.5, 132.4, 124.9, 121.4, 114.8, 110.0, 109.1, 108.0, 100.7,
74.4, 55.5, 37.9, 30.9, 22.6 (2x).
4.3.10. 2-Allyl-3-(cyclopentyloxy)-1-(3,4-dimethoxybenzyl)-4-
methoxybenzene (7j). According to the general procedure,
reaction was performed in the presence of BF3·OEt2 (71 mg, 0.5
mmol), 5d (262 mg, 1.0 mmol) and 6a (180 mg, 1.3 mmol) in
CH2Cl2 (8 mL) at 25 oC for 2 h. Purification on silica gel
(hexanes/EtOAc = 4/1) afforded 7j (95%, 363 mg). Colorless
gum; HRMS (ESI, M++Na) calcd for C24H30O4Na 405.2033,
1
found 405.2037; H NMR (400 MHz, CDCl3): δ 6.78 (d, J = 8.8
Hz, 1H), 6.73 (br s, 2H), 6.64-6.62 (m, 2H), 5.94-5.84 (m, 1H),
4.98 (dq, J = 1.6, 10.4 Hz, 1H), 4.91 (dq, J = 1.6, 17.2 Hz, 1H),
4.88-4.85 (m, 1H), 3.89 (s, 2H), 3.85 (s, 3H), 3.82 (s, 3H), 3.80 (s,
3H), 3.40 (dt, J = 1.6, 6.0 Hz, 2H), 1.90-1.78 (m, 4H), 1.76-1.69
(m, 2H), 1.59-1.55 (m, 2H); 13C NMR (100 MHz, CDCl3): δ
151.1, 148.8, 147.1, 145.4, 136.6, 133.7, 132.43, 132.38, 124.7,
120.5, 114.7, 112.0, 111.1, 110.2, 84.2, 55.8, 55.7, 55.5, 37.7,
32.8 (2x), 30.9, 23.7 (2x).
4.3.7.
2-Allyl-3-butoxy-1-(3,4-dimethoxybenzyl)-4-
methoxybenzene (7g). According to the general procedure,
reaction was performed in the presence of BF3·OEt2 (71 mg, 0.5
mmol), 5c (250 mg, 1.0 mmol) and 6a (180 mg, 1.3 mmol) in
CH2Cl2 (8 mL) at 25 oC for 2 h. Purification on silica gel
(hexanes/EtOAc = 4/1) afforded 7g (95%, 352 mg). Colorless
gum; HRMS (ESI, M++Na) calcd for C23H30O4Na 393.2033,
4.3.11.
2-Allyl-3-(cyclopentyloxy)-4-methoxy-1-(2,3,4-
trimethoxybenzyl)benzene (7k). According to the general
procedure, reaction was performed in the presence of BF3·OEt2
(71 mg, 0.5 mmol), 5d (262 mg, 1.0 mmol) and 6b (219 mg, 1.3
1
found 393.2035; H NMR (400 MHz, CDCl3): δ 6.78 (d, J = 8.0
Hz, 1H), 6.76 (d, J = 8.4 Hz, 1H), 6.73 (d, J = 8.4 Hz, 1H), 6.64
(s, 1H), 6.63 (d, J = 8.0 Hz, 1H), 5.97-5.87 (m, 1H), 4.99 (dq, J =
1.6, 10.0 Hz, 1H), 4.92 (dq, J = 1.6, 17.2 Hz, 1H), 3.94 (t, J = 6.8
Hz, 2H), 3.88 (s, 2H), 3.85 (s, 3H), 3.83 (s, 3H), 3.80 (s, 3H),
3.42 (dt, J = 1.6, 5.6 Hz, 2H), 1.79-1.72 (m, 2H), 1.55-1.47 (m,
2H), 0.97 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ
151.3, 148.8, 147.2, 146.7, 136.9, 133.6, 132.4, 132.1, 125.1,
120.6, 114.7, 112.1, 111.1, 110.1, 72.9, 55.8, 55.7, 55.6, 37.7,
32.4, 30.6, 19.1, 13.9.
o
mmol) in CH2Cl2 (8 mL) at 25 C for 2 h. Purification on silica
gel (hexanes/EtOAc = 4/1) afforded 7k (86%, 355 mg). Colorless
gum; HRMS (ESI, M++Na) calcd for C25H32O5Na 435.2138,
1
found 435.2141; H NMR (400 MHz, CDCl3): δ 6.71 (d, J = 8.4
Hz, 1H), 6.66 (d, J = 8.4 Hz, 1H), 6.60-6.55 (m, 2H), 5.94-5.86
(m, 1H), 4.98 (dq, J = 1.6, 10.4 Hz, 1H), 4.93 (dq, J = 1.6, 17.2
Hz, 1H), 4.88-4.84 (m, 1H), 3.89 (s, 2H), 3.86 (s, 3H), 3.83 (s,
3H), 3.80 (s, 3H), 3.76 (s, 3H), 3.45 (dt, J = 1.6, 6.0 Hz, 2H),
1.92-1.79 (m, 4H), 1.76-1.69 (m, 2H), 1.61-1.55 (m, 2H); 13C
NMR (100 MHz, CDCl3): δ 152.0, 151.7, 150.8, 142.2, 136.6,
132.4, 132.3, 127.1, 124.3, 124.0, 114.6, 110.1, 107.0, 105.1,
84.2, 60.6, 60.5, 55.8, 55.5, 32.7 (2x), 31.8, 30.8, 23.6 (2x).
4.3.8.
2-Allyl-3-butoxy-4-methoxy-1-(2,3,4-
trimethoxybenzyl)benzene (7h). According to the general
procedure, the reaction was performed in the presence of
BF3·OEt2 (71 mg, 0.5 mmol), 5c (250 mg, 1.0 mmol) and 6b
(219 mg, 1.3 mmol) in CH2Cl2 (8 mL) at 25 oC for 2 h.
Purification on silica gel (hexanes/EtOAc = 4/1) afforded 7h
(87%, 348 mg). Colorless gum; HRMS (ESI, M++Na) calcd for
C24H32O5Na 423.2138, found 423.2142; 1H NMR (400 MHz,
CDCl3): δ 6.72 (d, J = 8.4 Hz, 1H), 6.69 (d, J = 8.4 Hz, 1H), 6.60
(d, J = 8.8 Hz, 1H), 6.56 (d, J = 8.8 Hz, 1H), 5.98-5.89 (m, 1H),
4.99 (dq, J = 1.6, 10.0 Hz, 1H), 4.93 (dq, J = 1.6, 16.8 Hz, 1H),
3.94 (t, J = 6.4 Hz, 2H), 3.89 (s, 3H), 3.88 (s, 2H), 3.83 (s, 3H),
3.81 (s, 3H), 3.78 (s, 3H), 3.46 (dt, J = 1.6, 5.6 Hz, 2H), 1.80-
1.73 (m, 2H), 1.56-1.46 (m, 2H), 0.98 (t, J = 7.6 Hz, 3H); 13C
NMR (100 MHz, CDCl3): δ 152.0, 151.7, 151.1, 146.6, 142.2,
136.8, 132.3, 132.1, 127.0, 124.7, 124.1, 114.6, 110.0, 107.0,
72.8, 60.64, 60.55, 55.8, 55.5, 32.4, 31.7, 30.6, 19.1, 13.9.
4.3.12.
5-(2-Allyl-3-(cyclopentyloxy)-4-
methoxybenzyl)benzo[d][1,3]dioxole (7l). According to the
general procedure, the reaction was performed in the presence of
BF3·OEt2 (71 mg, 0.5 mmol), 5d (262 mg, 1.0 mmol) and 6c
(159 mg, 1.3 mmol) in CH2Cl2 (8 mL) at 25 oC for 2 h.
Purification on silica gel (hexanes/EtOAc = 4/1) afforded 7l
(93%, 341 mg). Colorless gum; HRMS (ESI, M++Na) calcd for
C23H26O4Na 389.1721, found 389.1725; 1H NMR (400 MHz,
CDCl3): δ 6.75-6.67 (m, 3H), 6.57 (s, 1H), 6.56-6.51 (m, 1H),
5.93-5.83 (m, 1H), 5.91 (s, 2H), 4.97 (dq, J = 1.6, 10.0 Hz, 1H),
4.90 (dq, J = 1.6, 17.2 Hz, 1H), 4.87-4.83 (m, 1H), 3.85 (s, 2H),
3.82 (s, 3H), 3.39 (dt, J = 1.6, 5.6 Hz, 2H), 1.97-1.77 (m, 4H),
1.76-1.69 (m, 2H), 1.59-1.55 (m, 2H); 13C NMR (100 MHz,
CDCl3): δ 151.2, 147.6, 145.6, 136.6, 135.1, 132.41, 132.38,

8
Tetrahedron
124.8, 124.1, 121.4, 114.8, 110.2, 109.2, 108.0, 100.7, 84.3,
J = 1.2, 6.0 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 148.7,
ACCEPTED MANUSCRIPT
55.6, 37.9, 32.8 (2x), 30.9, 23.7 (2x).
147.2, 147.1, 147.0, 133.5, 131.1, 130.6, 129.6, 125.9, 120.4,
113.5, 112.9, 111.8, 111.0, 55.81, 55.80, 55.76, 55.65, 37.7, 35.6,
17.8.
4.3.13.
2-(But-3-en-2-yl)-1-(3,4-dimethoxybenzyl)-3,4-
dimethoxybenzene (7m). According to the general procedure,
the reaction was performed in the presence of BF3·OEt2 (71 mg,
0.5 mmol), 5e (222 mg, 1.0 mmol) and 6a (180 mg, 1.3 mmol) in
CH2Cl2 (8 mL) at 25 oC for 2 h. Purification on silica gel
(hexanes/EtOAc = 4/1) afforded 7m (96%, 329 mg). Colorless
gum; HRMS (ESI, M++Na) calcd for C21H26O4Na 365.1721,
4.3.17.
2-(But-2-en-1-yl)-3,4-dimethoxy-1-(2,3,4-
trimethoxybenzyl)benzene (7q). According to the general
procedure, the reaction was performed in the presence of
BF3·OEt2 (71 mg, 0.5 mmol), 5f (222 mg, 1.0 mmol) and 6b (219
mg, 1.3 mmol) in CH2Cl2 (8 mL) at 25 oC for 2 h. Purification on
silica gel (hexanes/EtOAc = 4/1) afforded 7q (92%, 343 mg).
Colorless gum; HRMS (ESI, M++Na) calcd for C22H28O5Na
1
found 365.1724; H NMR (400 MHz, CDCl3): δ 6.81-6.73 (m,
3H), 6.63 (s, 1H), 6.62 (d, J = 8.4 Hz, 1H), 6.20-6.12 (m, 1H),
4.93 (dt, J = 1.6, 10.4 Hz, 1H), 4.84 (dt, J = 1.6, 17.6 Hz, 1H),
3.97 (d, J = 16.0 Hz, 1H), 3.92 (d, J = 16.0 Hz, 1H), 3.85 (s, 3H),
3.84 (s, 3H), 3.84-3.83 (m, 1H), 3.82 (s, 3H), 3.80 (s, 3H), 1.32
(d, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 151.6, 148.7,
148.0, 147.1, 143.0, 137.9, 134.0, 131.2, 125.8, 120.5, 112.5,
112.0, 111.0, 110.1, 60.5, 55.8, 55.7, 55.5, 38.7, 37.1, 18.9.
1
395.1826, found 395.1830; H NMR (400 MHz, CDCl3): δ 6.69
(s, 1H), 5.59 (s, 1H), 6.55 (br s, 2H), 5.55-5.47 (m, 1H), 5.44-
5.35 (m, 1H), 3.87 (s, 3H), 3.86 (s, 2H), 3.85 (s, 3H), 3.81 (s, 3H),
3.80 (s, 3H), 3.76 (s, 3H), 3.23 (d, J = 6.0 Hz, 2H), 1.64 (d, J =
6.0 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 151.9, 151.6, 147.1,
146.9, 142.1, 131.1, 130.5, 129.7, 126.9, 125.7, 123.8, 113.5,
112.7, 106.9, 60.6, 60.5, 55.8, 55.74, 55.71, 35.6, 31.7, 17.7.
4.3.14.
2-(But-3-en-2-yl)-3,4-dimethoxy-1-(2,3,4-
trimethoxybenzyl)benzene (7n). According to the general
procedure, the reaction was performed in the presence of
BF3·OEt2 (71 mg, 0.5 mmol), 5e (222 mg, 1.0 mmol) and 6b
(219 mg, 1.3 mmol) in CH2Cl2 (8 mL) at 25 oC for 2 h.
Purification on silica gel (hexanes/EtOAc = 4/1) afforded 7n
(90%, 335 mg). Colorless gum; HRMS (ESI, M++Na) calcd for
C22H28O5Na 395.1826, found 395.1828; 1H NMR (400 MHz,
CDCl3): δ 6.75 (d, J = 8.4 Hz, 1H), 6.72 (d, J = 8.4 Hz, 1H), 6.55
(br s, 2H), 6.21-6.13 (m, 1H), 4.93 (dt, J = 1.6, 10.4 Hz, 1H),
4.87 (dt, J = 1.6, 17.2 Hz, 1H), 3.95 (d, J = 16.0 Hz, 1H), 3.90 (d,
J = 16.0 Hz, 1H), 3.89 (s, 3H), 3.87-3.85 (m, 1H), 3.83 (br s, 6H),
3.82 (s, 3H), 3.81 (s, 3H), 1.33 (d, J = 7.2 Hz, 3H); 13C NMR
(100 MHz, CDCl3): δ 151.9, 151.5, 151.4, 143.0, 137.8, 131.2,
127.3, 125.6, 124.1, 123.5, 112.4, 110.0, 106.9, 105.1, 60.6,
60.51, 60.45, 55.8, 55.4, 36.9, 32.5, 18.7.
4.3.18.
2-Allyl-1-(3,4-diisopropoxybenzyl)-3,4-
dimethoxybenzene (7r). According to the general procedure, the
reaction was performed in the presence of BF3·OEt2 (71 mg, 0.5
mmol), 5a (208 mg, 1.0 mmol) and 6d (253 mg, 1.3 mmol) in
CH2Cl2 (8 mL) at 25 oC for 2 h. Purification on silica gel
(hexanes/EtOAc = 4/1) afforded 7r (94%, 361 mg). Colorless
gum; HRMS (ESI, M++Na) calcd for C24H32O4Na 407.2189,
1
found 407.2195; H NMR (400 MHz, CDCl3): δ 6.82 (d, J = 8.0
Hz, 1H), 6.79 (d, J = 8.4 Hz, 1H), 6.75 (d, J = 8.4 Hz, 1H), 6.67
(d, J = 2.0 Hz, 1H), 6.63 (dd, J = 2.0, 8.0 Hz, 1H), 5.94-5.85 (m,
1H), 4.98 (dq, J = 1.6, 10.0 Hz, 1H), 4.90 (2.0, 17.2 Hz, 1H),
4.45-4.38 (m, 2H), 3.85 (br s, 5H), 3.81 (s, 3H), 3.41 (dt, J = 1.6,
6.0 Hz, 2H), 1.32 (d, J = 6.0 Hz, 6H), 1.29 (d, J = 6.0 Hz, 6H);
13C NMR (100 MHz, CDCl3): δ 151.1, 149.0, 147.4, 147.2, 136.8,
134.6, 132.5, 132.1, 125.4, 121.8, 119.0, 118.4, 114.8, 110.1,
72.2, 72.0, 60.7, 55.6, 37.7, 30.5, 22.22 (2x), 22.16 (2x).
4.3.15.
5-(2-(But-3-en-2-yl)-3,4-
dimethoxybenzyl)benzo[d][1,3]dioxole (7o). According to the
general procedure, the reaction was performed in the presence of
BF3·OEt2 (71 mg, 0.5 mmol), 5e (222 mg, 1.0 mmol) and 6c (159
mg, 1.3 mmol) in CH2Cl2 (8 mL) at 25 oC for 2 h. Purification on
silica gel (hexanes/EtOAc = 4/1) afforded 7o (94%, 307 mg).
Colorless gum; HRMS (ESI, M++Na) calcd for C20H22O4Na
4.3.19.
2-Allyl-1-(4-isopropoxy-3-methoxybenzyl)-3,4-
dimethoxybenzene (7s) and 2-Allyl-1-(3-isopropoxy-4-
methoxybenzyl)-3,4-dimethoxybenzene (7t). According to the
general procedure, the reaction was performed in the presence of
BF3·OEt2 (71 mg, 0.5 mmol), 5a (208 mg, 1.0 mmol) and 6e (216
mg, 1.3 mmol) in CH2Cl2 (8 mL) at 25 oC for 2 h. Purification on
silica gel (hexanes/EtOAc = 4/1) afforded a mixture of 7s and 7t
(94%, 335 mg) with a ratio of 2:1. HRMS (ESI, M++Na) calcd
1
349.1409, found 349.1412; H NMR (400 MHz, CDCl3): δ 6.80
(d, J = 8.4 Hz, 1H), 6.75 (d, J = 8.4 Hz, 1H), 6.72 (d, J = 7.6 Hz,
1H), 6.58 (d, J = 1.2 Hz, 1H), 6.56 (d, J = 7.6 Hz, 1H), 6.18-6.10
(m, 1H), 5.91 (s, 2H), 4.93 (dt, J = 1.6, 10.4 Hz, 1H), 4.84 (dt, J
= 1.6, 17.2 Hz, 1H), 3.94 (d, J = 16.0 Hz, 1H), 3.88 (d, J = 16.0
Hz, 1H), 3.85 (s, 3H), 3.84-3.82 (m, 1H), 3.81 (s, 3H), 1.30 (d, J
= 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 151.8, 148.1,
147.6, 145.6, 143.1, 137.9, 135.4, 131.2, 126.0, 121.4, 112.5,
110.2, 109.1, 108.0, 100.7, 60.6, 55.6, 38.9, 37.1, 18.9.
1
for C22H28O4Na 379.1877, found 379.1881; H NMR (400 MHz,
CDCl3): δ 6.82-6.77 (m, 3H), 6.67-6.59 (m, 2H), 5.97-5.87 (m,
1H), 5.01-4.90 (m, 2H), 4.51-4.42 (m, 1H), 3.88 (s, 2H), 3.85 (s,
3H), 3.83 (s, 3H), 3.79 (s, 3H), 3.45-3.43 (m, 2H), 1.37-1.32 (m,
6H).
4.3.20.
2-Allyl-1-(4-(benzyloxy)-3-methoxybenzyl)-3,4-
dimethoxybenzene (7u) and 2-Allyl-1-(3-(benzyloxy)-4-
methoxybenzyl)-3,4-dimethoxybenzene (7v). According to the
general procedure, the reaction was performed in the presence of
BF3·OEt2 (71 mg, 0.5 mmol), 5a (208 mg, 1.0 mmol) and 6f (279
mg, 1.3 mmol) in CH2Cl2 (8 mL) at 25 oC for 2 h. Purification on
silica gel (hexanes/EtOAc = 4/1) afforded a mixture of 7u and 7v
(92%, 372 mg) with a ratio of 1:1. HRMS (ESI, M++Na) calcd
4.3.16.
2-(But-2-en-1-yl)-1-(3,4-dimethoxybenzyl)-3,4-
dimethoxybenzene (7p). According to the general procedure, the
reaction was performed in the presence of BF3·OEt2 (71 mg, 0.5
mmol), 5f (222 mg, 1.0 mmol) and 6a (180 mg, 1.3 mmol) in
CH2Cl2 (8 mL) at 25 oC for 2 h. Purification on silica gel
(hexanes/EtOAc = 4/1) afforded 7p (95%, 325 mg). Colorless
o
1
solid; mp = 71-72 C (recrystallized from hexanes and EtOAc);
for C26H28O4Na 427.1877, found 427.1882; H NMR (400 MHz,
HRMS (ESI, M++Na) calcd for C21H26O4Na 365.1721, found
CDCl3): δ 7.46-7.28 (m, 4H), 6.83-6.75 (m, 3H), 6.70-6.66 (m,
3H), 5.98-5.84 (m, 1H), 5.14 (s, 1H), 5.10 (s, 1H), 5.03-4.86 (m,
2H), 3.87 (s, 3H), 3.86 (s, 3H), 3.84 (s, 3H), 3.83 (s, 2H), 3.44 (dt,
J = 1.6, 5.6 Hz, 1H), 3.36 (dt, J = 1.6, 5.6 Hz, 1H).
1
365.1726; H NMR (400 MHz, CDCl3): δ 6.77 (d, J = 8.4 Hz,
1H), 6.70 (s, 1H), 6.65-6.60 (m, 2H), 6.61 (s, 1H), 5.54-5.46 (m,
1H), 5.44-5.36 (m, 1H), 3.89 (s, 2H), 3.86 (s, 3H), 3.84 (s, 3H),
3.80 (s, 3H), 3.78 (s, 3H), 3.21 (dt, J = 1.2, 6.0 Hz, 2H), 1.65 (dq,

4.3.25.
2-Butoxy-1-methoxy-3-(prop-1-en-1-yl)-4-(2,3,4-
4.3.21. 1-(3,4-Dimethoxybenzyl)-3,4-dimethoxy-2-(prop-1-en-
ACCEPTED MANUSCRIPT
trimethoxybenzyl)benzene (11e). According to the general
1-yl)benzene (11a). According to the general procedure, the
reaction was performed in the presence of BF3·OEt2 (71 mg, 0.5
mmol), 10a (208 mg, 1.0 mmol) and 6a (180 mg, 1.3 mmol) in
CH2Cl2 (8 mL) at 25 oC for 2 h. Purification on silica gel
(hexanes/EtOAc = 4/1) afforded 11a (90%, 296 mg). Colorless
gum; HRMS (ESI, M++Na) calcd for C20H24O4Na 351.1565,
procedure, the reaction was performed in the presence of
BF3·OEt2 (71 mg, 0.5 mmol), 10c (250 mg, 1.0 mmol) and 6b
(219 mg, 1.3 mmol) in CH2Cl2 (8 mL) at 25 oC for 2 h.
Purification on silica gel (hexanes/EtOAc = 4/1) afforded 11e
(85%, 340 mg). Colorless gum; HRMS (ESI, M++Na) calcd for
C24H32O5Na 423.2138, found 423.2142; 1H NMR (400 MHz,
CDCl3): δ 7.01-6.97 (m, 1H), 6.73-6.66 (m, 2H), 6.59 (s, 1H),
6.57-6.56 (m, 2H), 6.36 (dq, J = 1.6, 16.0 Hz, 1H), 6.01 (dq, J =
6.4, 16.0 Hz, 1H), 3.89 (s, 3H), 3.86 (s, 3H), 3.82 (s, 3H), 3.81 (s,
3H), 3.77 (s, 2H), 1.84 (dd, J = 1.6, 6.4 Hz, 3H), 1.74-1.67 (m,
2H), 1.53-1.45 (m, 2H), 0.95 (t, J = 7.2 Hz, 3H); 13C NMR (100
MHz, CDCl3): δ 153.5, 151.9, 151.2, 146.2, 132.5, 131.4, 131.1,
127.6, 125.0, 124.7, 124.1, 123.6, 110.3, 107.0, 105.1, 72.3, 60.8,
60.5, 56.0, 55.9, 32.6, 32.3, 19.2, 13.8.
1
found 351.1566; H NMR (400 MHz, CDCl3): δ 6.79 (d, J = 8.4
Hz, 1H), 6.77 (d, J = 8.0 Hz, 1H), 6.73 (d, J = 8.4 Hz, 1H), 6.66
(d, J = 2.0 Hz, 1H), 6.62 (dd, J = 2.0, 8.0 Hz, 1H), 6.37 (dq, J =
1.6, 16.0 Hz, 1H), 6.06 (dq, J = 6.8, 16.0 Hz, 1H), 3.92 (s, 2H),
3.84 (s, 3H), 3.83 (s, 3H), 3.81 (s, 3H), 3.74 (s, 3H), 1.87 (dd, J =
1.6, 6.4 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 151.1, 148.7,
147.0, 146.9, 133.9, 131.9, 131.6, 131.2, 125.3, 124.3, 120.5,
112.0, 111.0, 110.3, 59.8, 55.7, 55.6 (2x), 38.4, 19.2.
4.3.22.
1-(3,4-Dimethoxy-2-(prop-1-en-1-yl)benzyl)-2,3,4-
4.4. A representative synthetic procedure of skeletons 1 and
13 is as follows:
trimethoxybenzene (11b). According to the general procedure,
the reaction was performed in the presence of BF3·OEt2 (71 mg,
0.5 mmol), 10a (208 mg, 1.0 mmol) and 6b (219 mg, 1.3 mmol)
A solution of 2.5% osmium (OsO4, 0.6 mL, in THF) was
added to a solution of skeleton 7, 11 (0.6 mmol) in cosolvent of
THF (6 mL) and water (6 mL). N-Methylmorpholine-N-oxide
(NMO, 50% in water, 300 mg, 1.3 mmol) was added to the
o
in CH2Cl2 (8 mL) at 25 C for 2 h. Purification on silica gel
(hexanes/EtOAc = 4/1) afforded 11b (86%, 308 mg). Colorless
gum; HRMS (ESI, M++Na) calcd for C21H26O5Na 381.1670,
o
reaction mixture at 25 C. The reaction mixture was stirred at 25
1
found 381.1672; H NMR (400 MHz, CDCl3): δ 6.74 (d, J = 8.8
oC for 2 h. Then, sodium periodate (NaIO4, 150 mg, 0.7 mmol)
was added to the reaction mixture at 25 oC. The reaction mixture
was stirred at 25 oC for 1 h. The reaction mixture was
concentrated and the residue was diluted with water (10 mL) and
the mixture was extracted with CH2Cl2 (3 x 20 mL). The
combined organic layers were washed with brine, dried, filtered
and evaporated to afford crude product under reduced pressure.
Next, BF3·OEt2 (71mg, 0.5 mmol) was added to a solution of the
crude product 8, 12 without further purification in CH2Cl2 (8 mL)
Hz, 1H), 6.71 (d, J = 8.4 Hz, 1H), 6.58 (d, J = 8.4 Hz, 1H), 6.56
(d, J = 8.8 Hz, 1H), 638 (dq, J = 1.6, 16.0 Hz, 1H), 6.05 (dq, J =
6.8 Hz, 16.0 Hz, 1H), 3.90 (s, 2H), 3.88 (s, 3H), 3.83 (s, 3H),
3.82 (s, 3H), 3.79 (s, 3H), 3.75 (s, 3H), 1.86 (dd, J = 1.6, 6.4 Hz,
3H); 13C NMR (100 MHz, CDCl3): δ 151.9, 151.6, 151.0, 146.9,
142.1, 132.0, 131.5, 131.1, 127.5, 125.3, 124.4, 124.1, 110.2,
107.0, 60.7, 60.5, 59.9, 55.8, 55.7, 32.5, 19.3.
4.3.23. 1-(3,4-Dimethoxybenzyl)-3-isopropoxy-4-methoxy-2-
(prop-1-en-1-yl)benzene (11c). According to the general
procedure, the reaction was performed in the presence of
BF3·OEt2 (71 mg, 0.5 mmol), 10b (236 mg, 1.0 mmol) and 6a
(180 mg, 1.3 mmol) in CH2Cl2 (8 mL) at 25 oC for 2 h.
Purification on silica gel (hexanes/EtOAc = 4/1) afforded 11c
(87%, 310 mg). Colorless gum; HRMS (ESI, M++Na) calcd for
C22H28O4Na 379.1877, found 379.1880; 1H NMR (400 MHz,
CDCl3): δ 6.77 (d, J = 8.0 Hz, 1H), 6.76 (d, J = 8.4 Hz, 1H), 6.71
(d, J = 8.8 Hz, 1H), 6.63 (s, 1H), 6.62 (d, J = 7.6 Hz, 1H), 6.34
(dq, J = 1.6, 16.0 Hz, 1H), 6.01 (dq, J = 6.4, 16.0 Hz, 1H), 4.37-
4.31 (m, 1H), 3.92 (s, 2H), 3.85 (s, 3H), 3.81 (s, 3H), 3.80 (s, 3H),
1.84 (dd, J = 1.6, 6.4 Hz, 3H), 1.23 (d, J = 6.4 Hz, 6H); 13C NMR
(100 MHz, CDCl3): δ 151.6, 148.7, 147.0, 145.0, 134.2, 133.1,
131.5, 131.3, 125.4, 124.9, 120.6, 112.0, 111.1, 110.2, 74.9, 55.8,
55.7 (2x), 38.6, 22.4 (2x), 19.1.
o
o
at 25 C. The reaction mixture was stirred at 25 C for 2 h. The
overall synthetic procedure had to be monitored by TLC until the
reaction was completed. The reaction mixture was concentrated
and the residue was diluted with water (10 mL) and the mixture
was extracted with CH2Cl2 (3 x 20 mL). The combined organic
layers were washed with brine, dried, filtered and evaporated to
afford crude product under reduced pressure. Purification on
silica gel (hexanes/EtOAc = 6/1) afforded 1a-1v and 13a-13e.
4.4.1. 1,2,7,8-Tetramethoxy-5H-dibenzo[a,d][7]annulene (1a).
According to the general procedure, the reaction was performed
in two-step including (i) OsO4 (2.5%, 0.6 mL in THF), NMO
(50% in water, 300 mg, 1.3 mmol), NaIO4 (150 mg, 0.7 mmol)
and 7a (197 mg, 0.6 mmol) in the cosolvent of THF (6 mL) and
o
water (6 mL) at 25 C for 3 h, (ii) BF3·OEt2 (71 mg, 0.5 mmol)
and in situ-generated 8a without further purification in CH2Cl2 (8
mL) at 25 oC for 2 h. Purification on silica gel (hexanes/EtOAc =
o
4.3.24. 2-Isopropoxy-1-methoxy-3-(prop-1-en-1-yl)-4-(2,3,4-
trimethoxybenzyl)benzene (11d). According to the general
procedure, the reaction was performed in the presence of
BF3·OEt2 (71 mg, 0.5 mmol), 10b (236 mg, 1.0 mmol) and 6b
(219 mg, 1.3 mmol) in CH2Cl2 (8 mL) at 25 oC for 2 h.
Purification on silica gel (hexanes/EtOAc = 4/1) afforded 11d
(88%, 340 mg). Colorless gum; HRMS (ESI, M++Na) calcd for
C23H30O5Na 409.1982, found 409.1985; 1H NMR (400 MHz,
CDCl3): δ 6.70 (s, 1H), 6.59 (s, 1H), 6.57 (d, J = 8.4 Hz, 1H),
6.54 (d, J = 8.4 Hz, 1H), 6.36 (dd, J = 1.6, 16.0 Hz, 1H), 5.99 (dq,
J = 6.4, 16.0 Hz, 1H), 4.37-4.30 (m, 1H), 3.88 (s, 2H), 3.85 (s,
3H), 3.82 (s, 3H), 3.79 (s, 3H), 3.76 (s, 3H), 1.83 (dd, J = 1.6, 6.4
Hz, 3H), 1.23 (d, J = 6.0 Hz, 6H); 13C NMR (100 MHz, CDCl3):
δ 153.4, 151.9, 151.3, 142.2, 133.1, 131.1, 127.8, 125.4, 124.8,
124.1, 123.6, 110.1, 107.0, 105.1, 74.8, 60.7, 60.5, 56.0, 55.6,
32.6, 22.4 (2x), 19.1.
6/1) afforded 1a (88%, 165 mg). Colorless solid; mp = 57-58 C
(recrystallized from hexanes and EtOAc); HRMS (ESI, M++Na)
1
calcd for C19H20O4Na 335.1253, found 335.1254; H NMR (400
MHz, CDCl3): δ 7.25 (d, J = 12.0 Hz, 1H), 7.00 (d, J = 12.0 Hz,
1H), 6.98 (d, J = 8.0 Hz, 1H), 6.87 (d, J = 8.4 Hz, 1H), 6.79 (br s,
2H), 3.91 (s, 3H), 3.86 (s, 3H), 3.83 (s, 3H), 3.81 (s, 3H), 3.60 (s,
2H); 13C NMR (100 MHz, CDCl3): δ 150.7, 149.5, 147.2, 146.1,
132.8, 131.53, 131.47, 129.4, 127.9, 124.8, 122.6, 112.6, 111.1,
110.8, 60.7, 56.02, 56.00, 55.9, 40.5.
4.4.2.
1,2,6,7,8-Pentamethoxy-5H-dibenzo[a,d][7]annulene
(1b). According to the general procedure, the reaction was
performed in two-step including (i) OsO4 (2.5%, 0.6 mL in THF),
NMO (50% in water, 300 mg, 1.3 mmol), NaIO4 (150 mg, 0.7
mmol) and 7b (215 mg, 0.6 mmol) in the cosolvent of THF (6
mL) and water (6 mL) at 25 oC for 3 h, (ii) BF3·OEt2 (71 mg, 0.5

10
Tetrahedron
ACCEPTED MANUSCRIPT
mmol) and in situ-generated 8b without further purification in
6.95 (d, J = 12.0 Hz, 1H), 6.86 (d, J = 8.4 Hz, 1H), 6.60 (s, 1H),
CH2Cl2 (8 mL) at 25 oC for 2 h. Purification on silica gel
(hexanes/EtOAc = 6/1) afforded 1b (89%, 183 mg). Colorless
solid; mp = 119-120 oC (recrystallized from hexanes and EtOAc);
HRMS (ESI, M++Na) calcd for C20H22O5Na 365.1358, found
4.43-4.37 (m, 1H), 3.93 (s, 3H), 3.89 (s, 3H), 3.83 (s, 3H), 3.80 (s,
3H), 3.66 (br s, 2H), 1.30 (d, J = 6.4 Hz, 6H); 13C NMR (100
MHz, CDCl3): δ 151.1, 150.9, 150.0, 144.4, 142.7, 133.2, 131.5,
130.9, 130.6, 127.1, 125.5, 122.5, 112.6, 107.0, 75.5, 61.5, 60.9,
55.99, 55.97, 31.4, 22.7 (2x).
1
365.1360; H NMR (400 MHz, CDCl3): δ 7.28 (d, J = 12.0 Hz,
1H), 7.04 (d, J = 8.4 Hz, 1H), 6.99 (d, J = 12.0 Hz, 1H), 6.88 (d,
J = 8.4 Hz, 1H), 6.62 (s, 1H), 3.92 (s, 3H), 3.88 (s, 3H), 3.83 (s,
6H), 3.82 (s, 3H), 3.67 (s, 2H); 13C NMR (100 MHz, CDCl3): δ
151.2, 150.7, 150.0, 146.1, 142.9, 133.1, 131.6, 131.4, 129.7,
125.8, 125.3, 123.0, 112.6, 107.1, 61.5, 60.9, 60.7, 56.0 (2x),
31.3.
4.4.6.
9-Isopropoxy-8-methoxy-5H-
benzo[4',5']cyclohepta[1',2':4,5]benzo[1,2-d][1,3]dioxole (1f).
According to the general procedure, the reaction was performed
in two-step including (i) OsO4 (2.5%, 0.6 mL in THF), NMO
(50% in water, 300 mg, 1.3 mmol), NaIO4 (150 mg, 0.7 mmol)
and 7f (204 mg, 0.6 mmol) in the cosolvent of THF (6 mL) and
o
4.4.3.
8,9-Dimethoxy-5H-
water (6 mL) at 25 C for 3 h, (ii) BF3·OEt2 (71 mg, 0.5 mmol)
benzo[4',5']cyclohepta[1',2':4,5]benzo[1,2-d][1,3]dioxole (1c).
According to the general procedure, the reaction was performed
in two-step including (i) OsO4 (2.5%, 0.6 mL in THF), NMO
(50% in water, 300 mg, 1.3 mmol), NaIO4 (150 mg, 0.7 mmol)
and 7c (187 mg, 0.6 mmol) in the cosolvent of THF (6 mL) and
and in situ-generated 8f without further purification in CH2Cl2 (8
mL) at 25 oC for 2 h. Purification on silica gel (hexanes/EtOAc =
o
6/1) afforded 1f (90%, 175 mg). Colorless solid; mp = 86-87 C
(recrystallized from hexanes and EtOAc); HRMS (ESI, M++Na)
1
calcd for C20H20O4Na 347.1253, found 347.1255; H NMR (400
o
water (6 mL) at 25 C for 3 h, (ii) BF3·OEt2 (71 mg, 0.5 mmol)
MHz, CDCl3): δ 7.27 (d, J = 12.0 Hz, 1H), 6.93 (d, J = 8.4 Hz,
1H), 6.91 (d, J = 12.0 Hz, 1H), 6.86 (d, J = 8.4 Hz, 1H), 6.78 (s,
1H), 6.74 (s, 1H), 5.91 (s, 2H), 4.43-4.37 (m, 1H), 3.80 (s, 3H),
3.55 (s, 2H), 1.29 (d, J = 6.4 Hz, 6H); 13C NMR (100 MHz,
CDCl3): δ 151.0, 147.9, 145.9, 144.2, 132.9, 132.8, 130.8, 130.2,
129.1, 126.2, 121.9, 112.6, 107.9, 107.7, 101.0, 75.5, 56.0, 40.7,
22.6 (2x).
and in situ-generated 8c without further purification in CH2Cl2 (8
mL) at 25 oC for 2 h. Purification on silica gel (hexanes/EtOAc =
o
6/1) afforded 1c (90%, 160 mg). Colorless solid; mp = 90-91 C
(recrystallized from hexanes and EtOAc); HRMS (ESI, M++Na)
1
calcd for C18H16O4Na 319.0941, found 319.0942; H NMR (400
MHz, CDCl3): δ 7.24 (d, J = 12.0 Hz, 1H), 6.96 (d, J = 8.4 Hz,
1H), 6.95 (d, J = 12.0 Hz, 1H), 6.87 (d, J = 8.4 Hz, 1H), 6.77 (s,
1H), 6.75 (s, 1H), 5.91 (s, 2H), 3.83 (s, 3H), 3.81 (s, 3H), 3.55 (s,
2H); 13C NMR (100 MHz, CDCl3): δ 150.8, 148.1, 146.04,
146.00, 132.8, 132.7, 131.5, 129.3, 129.0, 124.9, 122.5, 112.7,
108.0, 107.9, 101.0, 60.7, 56.0, 40.6.
4.4.7. 1-Butoxy-2,7,8-trimethoxy-5H-dibenzo[a,d][7]annulene
(1g). According to the general procedure, the reaction was
performed in two-step including (i) OsO4 (2.5%, 0.6 mL in THF),
NMO (50% in water, 300 mg, 1.3 mmol), NaIO4 (150 mg, 0.7
mmol) and 7g (222 mg, 0.6 mmol) in the cosolvent of THF (6
mL) and water (6 mL) at 25 oC for 3 h, (ii) BF3·OEt2 (71 mg, 0.5
mmol) and in situ-generated 8g without further purification in
CH2Cl2 (8 mL) at 25 oC for 2 h. Purification on silica gel
(hexanes/EtOAc = 6/1) afforded 1g (91%, 194 mg). Colorless
4.4.4.
1-Isopropoxy-2,7,8-trimethoxy-5H-
dibenzo[a,d][7]annulene (1d). According to the general
procedure, the reaction was performed in two-step including (i)
OsO4 (2.5%, 0.6 mL in THF), NMO (50% in water, 300 mg, 1.3
mmol), NaIO4 (150 mg, 0.7 mmol) and 7d (214 mg, 0.6 mmol) in
o
solid; mp = 97-98 C (recrystallized from hexanes and EtOAc);
o
the cosolvent of THF (6 mL) and water (6 mL) at 25 C for 3 h,
HRMS (ESI, M++Na) calcd for C22H26O4Na 377.1721, found
1
(ii) BF3·OEt2 (71 mg, 0.5 mmol) and in situ-generated 8d without
further purification in CH2Cl2 (8 mL) at 25 oC for 2 h.
Purification on silica gel (hexanes/EtOAc = 6/1) afforded 1d
377.1722; H NMR (400 MHz, CDCl3): δ 7.28 (d, J = 12.0 Hz,
1H), 6.98 (d, J = 12.0 Hz, 1H), 6.97 (d, J = 8.4 Hz, 1H), 6.87 (d,
J = 8.0 Hz, 1H), 6.80 (br s, 2H), 3.92 (t, J = 7.2 Hz, 2H), 3.91 (s,
3H), 3.86 (s, 3H), 3.81 (s, 3H), 3.60 (s, 2H), 1.82-1.75 (m, 2H),
1.59-1.49 (m, 2H), 1.00 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): δ 150.8, 149.4, 147.1, 145.5, 132.8, 131.5, 131.2, 129.5,
127.9, 125.2, 122.3, 112.7, 111.1, 110.8, 73.1, 56.1, 56.0, 55.9,
40.5, 32.3, 19.2, 13.9.
o
(92%, 188 mg). Colorless solid; mp = 98-99 C (recrystallized
from hexanes and EtOAc); HRMS (ESI, M++Na) calcd for
C21H24O4Na 363.1565, found 363.1568; 1H NMR (400 MHz,
CDCl3): δ 7.28 (d, J = 12.0 Hz, 1H), 6.96 (d, J = 12.0 Hz, 1H),
6.95 (d, J = 8.4 Hz, 1H), 6.86 (d, J = 8.4 Hz, 1H), 6.80 (s, 1H),
6.79 (s, 1H), 4.43-4.37 (m, 1H), 3.91 (s, 3H), 3.85 (s, 3H), 3.80 (s,
3H), 3.59 (s, 2H), 1.29 (d, J = 6.0 Hz, 6H); 13C NMR (100 MHz,
CDCl3): δ 151.0, 149.3, 147.1, 144.3, 133.0, 131.6, 130.8, 130.2,
128.0, 126.0, 122.0, 112.5, 111.1, 110.8, 75.5, 56.0 (2x), 55.9,
40.6, 22.6 (2x).
4.4.8.
1-Butoxy-2,6,7,8-tetramethoxy-5H-
dibenzo[a,d][7]annulene (1h). According to the general
procedure, the reaction was performed in two-step including (i)
OsO4 (2.5%, 0.6 mL in THF), NMO (50% in water, 300 mg, 1.3
mmol), NaIO4 (150 mg, 0.7 mmol) and 7h (240 mg, 0.6 mmol) in
o
4.4.5.
1-Isopropoxy-2,6,7,8-tetramethoxy-5H-
the cosolvent of THF (6 mL) and water (6 mL) at 25 C for 3 h,
dibenzo[a,d][7]annulene (1e). According to the general
procedure, the reaction was performed in two-step including (i)
OsO4 (2.5%, 0.6 mL in THF), NMO (50% in water, 300 mg, 1.3
mmol), NaIO4 (150 mg, 0.7 mmol) and 7e (232 mg, 0.6 mmol) in
(ii) BF3·OEt2 (71 mg, 0.5 mmol) and in situ-generated 8h without
further purification in CH2Cl2 (8 mL) at 25 oC for 2 h.
Purification on silica gel (hexanes/EtOAc = 6/1) afforded 1h
(86%, 198 mg). Colorless gum; HRMS (ESI, M++Na) calcd for
C23H28O5Na 407.1826, found 407.1829; 1H NMR (400 MHz,
CDCl3): δ 7.29 (d, J = 12.0 Hz, 1H), 7.02 (d, J = 8.4 Hz, 1H),
6.97 (d, J = 12.0 Hz, 1H), 6.86 (d, J = 8.4 Hz, 1H), 6.61 (s, 1H),
3.92 (t, J = 7.2 Hz, 2H), 3.90 (s, 3H), 3.88 (s, 3H), 3.83 (s, 3H),
3.81 (s, 3H), 3.66 (br s, 2H), 1.81-1.74 (m, 2H), 1.58-1.48 (m,
2H), 0.99 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ
151.1, 150.8, 150.0, 145.6, 142.8, 133.1, 131.5, 131.3, 129.9,
o
the cosolvent of THF (6 mL) and water (6 mL) at 25 C for 3 h,
(ii) BF3·OEt2 (71 mg, 0.5 mmol) and in situ-generated 8e without
further purification in CH2Cl2 (8 mL) at 25 oC for 2 h.
Purification on silica gel (hexanes/EtOAc = 6/1) afforded 1e
(87%, 193 mg). Colorless gum; HRMS (ESI, M++Na) calcd for
C22H26O5Na 393.1670, found 393.1671; 1H NMR (400 MHz,
CDCl3): δ 7.30 (d, J = 12.0 Hz, 1H), 7.01 (d, J = 8.4 Hz, 1H),

126.3, 125.4, 122.7, 112.8, 107.0, 73.2, 61.5, 61.0, 56.1, 56.0,
32.4, 31.4, 19.2, 13.9.
in two-step including (i) OsO4 (2.5%, 0.6 mL in THF), NMO
(50% in water, 300 mg, 1.3 mmol), NaIO4 (150 mg, 0.7 mmol)
and 7l (220 mg, 0.6 mmol) in the cosolvent of THF (6 mL) and
ACCEPTED MANUSCRIPT
4.4.9.
9-Butoxy-8-methoxy-5H-
o
water (6 mL) at 25 C for 3 h, (ii) BF3·OEt2 (71 mg, 0.5 mmol)
benzo[4',5']cyclohepta[1',2':4,5]benzo[1,2-d][1,3]dioxole (1i).
According to the general procedure, the reaction was performed
in two-step including (i) OsO4 (2.5%, 0.6 mL in THF), NMO
(50% in water, 300 mg, 1.3 mmol), NaIO4 (150 mg, 0.7 mmol)
and 7i (213 mg, 0.6 mmol) in the cosolvent of THF (6 mL) and
and in situ-generated 8l without further purification in CH2Cl2 (8
mL) at 25 oC for 2 h. Purification on silica gel (hexanes/EtOAc =
6/1) afforded 1l (85%, 179 mg). Colorless solid; mp = 110-111
oC (recrystallized from hexanes and EtOAc); HRMS (ESI,
1
M++Na) calcd for C22H22O4Na 373.1409, found 373.1412; H
o
water (6 mL) at 25 C for 3 h, (ii) BF3·OEt2 (71 mg, 0.5 mmol)
NMR (400 MHz, CDCl3): δ 7.23 (d, J = 12.0 Hz, 1H), 6.92 (d, J
= 8.4 Hz, 1H), 6.91 (d, J = 12.0 Hz, 1H), 6.85 (d, J = 8.4 Hz, 1H),
6.77 (s, 1H), 6.74 (s, 1H), 5.91 (s, 2H), 4.79-4.76 (m, 1H), 3.80 (s,
3H), 3.54 (s, 2H), 1.91-1.84 (m, 4H), 1.71-1.54 (m, 4H); 13C
NMR (100 MHz, CDCl3): δ 150.9, 147.9, 145.9, 144.4, 132.9,
130.8, 130.1, 129.1, 126.1, 121.9, 112.9, 108.0, 107.7, 101.0,
85.0, 70.5, 56.1, 40.7, 32.8 (2x), 23.7 (2x). Single-crystal X-ray
diagram: crystal of 1l was grown by slow diffusion of EtOAc
into a solution of 1l in CH2Cl2 to yield colorless prisms. The
compound crystallizes in the triclinic crystal system, space group
P -1, a = 9.4510(6) Å, b = 9.7866(6) Å, c = 11.0042(7) Å, V =
895.19(10) Å3, Z = 2, dcalcd = 1.300 g/cm3, F(000) = 372, 2θ
range 2.02-26.38o, R indices (all data) R1 = 0.0600, wR2 =
0.1408.
and in situ-generated 8i without further purification in CH2Cl2 (8
mL) at 25 oC for 2 h. Purification on silica gel (hexanes/EtOAc =
6/1) afforded 1i (90%, 183 mg). Colorless gum; HRMS (ESI,
1
M++Na) calcd for C21H22O4Na 361.1409, found 361.1412; H
NMR (400 MHz, CDCl3): δ 7.28 (d, J = 12.0 Hz, 1H), 6.95 (d, J
= 8.8 Hz, 1H), 6.94 (d, J = 12.0 Hz, 1H), 6.87 (d, J = 8.0 Hz, 1H),
6.78 (s, 1H), 6.76 (s, 1H), 5.91 (s, 2H), 3.93 (t, J = 6.4 Hz, 2H),
3.82 (s, 3H), 3.55 (s, 2H), 1.82-1.75 (m, 2H), 1.59-1.50 (m, 2H),
1.00 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 150.8,
148.0, 145.9, 145.4, 132.8, 132.7, 131.2, 129.5, 129.0, 125.3,
122.2, 112.8, 107.9, 107.8, 101.0, 73.1, 56.1, 40.6, 32.3, 19.2,
13.9.
4.4.10.
1-(Cyclopentyloxy)-2,7,8-trimethoxy-5H-
dibenzo[a,d][7]annulene (1j). According to the general
procedure, the reaction was performed in two-step including (i)
OsO4 (2.5%, 0.6 mL in THF), NMO (50% in water, 300 mg, 1.3
mmol), NaIO4 (150 mg, 0.7 mmol) and 7j (230 mg, 0.6 mmol) in
4.4.13.
1,2,7,8-Tetramethoxy-11-methyl-5H-
dibenzo[a,d][7]annulene (1m). According to the general
procedure, the reaction was performed in two-step including (i)
OsO4 (2.5%, 0.6 mL in THF), NMO (50% in water, 300 mg, 1.3
mmol), NaIO4 (150 mg, 0.7 mmol) and 7m (205 mg, 0.6 mmol)
in the cosolvent of THF (6 mL) and water (6 mL) at 25 oC for 3 h,
(ii) BF3·OEt2 (71 mg, 0.5 mmol) and in situ-generated 8m
o
the cosolvent of THF (6 mL) and water (6 mL) at 25 C for 3 h,
(ii) BF3·OEt2 (71 mg, 0.5 mmol) and in situ-generated 8j without
further purification in CH2Cl2 (8 mL) at 25 oC for 2 h.
Purification on silica gel (hexanes/EtOAc = 6/1) afforded 1j
o
without further purification in CH2Cl2 (8 mL) at 25 C for 2 h.
o
(92%, 202 mg). Colorless solid; mp = 104-105 C (recrystallized
Purification on silica gel (hexanes/EtOAc = 6/1) afforded 1m
(91%, 178 mg). Colorless gum; HRMS (ESI, M++Na) calcd for
C20H22O4Na 349.1409, found 349.1412; 1H NMR (400 MHz,
CDCl3): δ 6.96 (d, J = 8.4 Hz, 1H), 6.92 (d, J = 1.6 Hz, 1H), 6.83
(d, J = 8.4 Hz, 1H), 6.73 (s, 1H), 6.72 (s, 1H), 3.88 (s, 3H), 3.83
(s, 3H), 3.81 (s, 3H), 3.72 (s, 3H), 3.52 (d, J = 13.2 Hz, 1H), 3.48
(d, J = 13.2 Hz, 1H), 2.45 (d, J = 1.6 Hz, 3H); 13C NMR (100
MHz, CDCl3): δ 151.2, 148.5, 147.04, 146.96, 136.4, 135.7,
133.1, 131.1, 130.0, 127.9, 121.6, 111.8, 110.7, 109.9, 60.2, 56.0,
55.94, 55.87, 40.3, 24.4.
from hexanes and EtOAc); HRMS (ESI, M++Na) calcd for
C23H26O4Na 389.1721, found 389.1722; 1H NMR (400 MHz,
CDCl3): δ 7.25 (d, J = 12.0 Hz, 1H), 6.96 (d, J = 12.0 Hz, 1H),
6.95 (d, J = 8.4 Hz, 1H), 6.86 (d, J = 8.4 Hz, 1H), 6.80 (s, 1H),
6.79 (s, 1H), 4.80-4.77 (m, 1H), 3.91 (s, 3H), 3.86 (s, 3H), 3.80 (s,
3H), 3.59 (s, 2H), 1.94-1.86 (m, 4H), 1.71-1.57 (m, 4H); 13C
NMR (100 MHz, CDCl3): δ 150.9, 149.3, 147.1, 144.5, 133.0,
131.6, 130.8, 130.1, 128.0, 125.9, 122.0, 112.8, 111.1, 110.8,
85.0, 56.05, 56.00, 55.9, 40.6, 32.8 (2x), 23.6 (2x).
4.4.11.
1-(Cyclopentyloxy)-2,6,7,8-tetramethoxy-5H-
4.4.14.
1,2,6,7,8-Pentamethoxy-11-methyl-5H-
dibenzo[a,d][7]annulene (1k). According to the general
procedure, the reaction was performed in two-step including (i)
OsO4 (2.5%, 0.6 mL in THF), NMO (50% in water, 300 mg, 1.3
mmol), NaIO4 (150 mg, 0.7 mmol) and 7k (248 mg, 0.6 mmol) in
dibenzo[a,d][7]annulene (1n). According to the general
procedure, the reaction was performed in two-step including (i)
OsO4 (2.5%, 0.6 mL in THF), NMO (50% in water, 300 mg, 1.3
mmol), NaIO4 (150 mg, 0.7 mmol) and 7n (223 mg, 0.6 mmol) in
o
the cosolvent of THF (6 mL) and water (6 mL) at 25 C for 3 h,
o
the cosolvent of THF (6 mL) and water (6 mL) at 25 C for 3 h,
(ii) BF3·OEt2 (71 mg, 0.5 mmol) and in situ-generated 8k without
further purification in CH2Cl2 (8 mL) at 25 oC for 2 h.
Purification on silica gel (hexanes/EtOAc = 6/1) afforded 1k
(84%, 200 mg). Colorless gum; HRMS (ESI, M++Na) calcd for
C24H28O5Na 419.1826, found 419.1830; 1H NMR (400 MHz,
CDCl3): δ 7.27 (d, J = 12.0 Hz, 1H), 7.00 (d, J = 8.4 Hz, 1H),
6.95 (d, J = 12.0 Hz, 1H), 6.86 (d, J = 8.4 Hz, 1H), 6.60 (s, 1H),
4.80-4.76 (m, 1H), 3.92 (s, 3H), 3.88 (s, 3H), 3.83 (s, 3H), 3.80 (s,
3H), 3.65 (br s, 2H), 1.94-1.89 (m, 4H), 1.71-1.56 (m, 4H); 13C
NMR (100 MHz, CDCl3): δ 151.1, 150.8, 150.0, 144.6, 142.8,
133.3, 131.5, 130.8, 130.5, 127.0, 125.5, 122.4, 112.8, 107.0,
85.0, 61.5, 61.0, 56.05, 56.02, 32.9 (2x), 31.5, 23.7 (2x).
(ii) BF3·OEt2 (71 mg, 0.5 mmol) and in situ-generated 8n without
further purification in CH2Cl2 (8 mL) at 25 oC for 2 h.
Purification on silica gel (hexanes/EtOAc = 6/1) afforded 1n
(82%, 175 mg). Colorless gum; HRMS (ESI, M++Na) calcd for
C21H24O5Na 379.1514, found 379.1515; 1H NMR (400 MHz,
CDCl3): δ 7.02 (d, J = 8.4 Hz, 1H), 6.91 (d, J = 1.6 Hz, 1H), 6.82
(d, J = 8.4 Hz, 1H), 6.54 (s, 1H), 4.12 (d, J = 12.8 Hz, 1H), 3.90
(s, 3H), 3.86 (s, 3H), 3.82 (s, 3H), 3.80 (s, 3H), 3.74 (s, 3H), 3.05
(d, J = 12.8 Hz, 1H), 2.45 (d, J = 1.2 Hz, 3H); 13C NMR (100
MHz, CDCl3): δ 151.2, 151.0, 149.4, 146.9, 141.8, 137.4, 135.7,
131.4, 130.0, 127.0, 123.7, 122.1, 111.8, 106.6, 61.4, 60.9, 60.3,
55.94, 55.93, 31.5, 24.5.
4.4.12.
9-(Cyclopentyloxy)-8-methoxy-5H-
4.4.15.
8,9-Dimethoxy-10-methyl-5H-
benzo[4',5']cyclohepta[1',2':4,5]benzo[1,2-d][1,3]dioxole (1l).
According to the general procedure, the reaction was performed
benzo[4',5']cyclohepta[1',2':4,5]benzo[1,2-d][1,3]dioxole (1o).
According to the general procedure, the reaction was performed

12
Tetrahedron
in two-step including (i) OsO (2.5%, 0.6 mL in THF), NMO
further purification in CH Cl (8 mL) at 25 oC for 2 h.
ACCEPTED MANUSCRIPT
4
2 2
(50% in water, 300 mg, 1.3 mmol), NaIO4 (150 mg, 0.7 mmol)
and 7o (196 mg, 0.6 mmol) in the cosolvent of THF (6 mL) and
water (6 mL) at 25 C for 3 h, (ii) BF3·OEt2 (71 mg, 0.5 mmol)
Purification on silica gel (hexanes/EtOAc = 6/1) afforded 1r
o
(95%, 210 mg). Colorless solid; mp = 99-100 C (recrystallized
from hexanes and EtOAc); HRMS (ESI, M++Na) calcd for
C23H28O4Na 391.1877, found 391.1880; 1H NMR (400 MHz,
CDCl3): δ 7.25 (d, J = 12.0 Hz, 1H), 6.98 (d, J = 8.4 Hz, 1H),
6.98 (d, J = 12.0 Hz, 1H), 6.89-6.85 (m, 3H), 4.56-4.50 (m, 1H),
4.44-4.38 (m, 1H), 3.84 (br s, 6H), 3.61 (s, 2H), 1.36 (d, J = 6.4
Hz, 6H), 1.33 (d, J = 6.4 Hz, 6H); 13C NMR (100 MHz, CDCl3):
δ 150.7, 149.8, 147.0, 146.0, 132.79, 132.75, 131.6, 129.4, 128.8,
124.4, 122.6, 118.4, 116.9, 112.3, 72.6, 72.0, 60.6, 55.9, 40.5,
22.22 (2x), 22.19 (2x).
o
and in situ-generated 8o without further purification in CH2Cl2 (8
mL) at 25 oC for 2 h. Purification on silica gel (hexanes/EtOAc =
6/1) afforded 1o (88%, 164 mg). Colorless gum; HRMS (ESI,
M++Na) calcd for C19H18O4Na 333.1097, found 333.1099; H
1
NMR (400 MHz, CDCl3): δ 6.94 (d, J = 8.4 Hz, 1H), 6.86 (d, J =
0.8 Hz, 1H), 6.83 (d, J = 8.4 Hz, 1H), 6.71 (s, 1H), 6.67 (s, 1H),
5.91 (d, J = 1.2 Hz, 1H), 5.83 (d, J = 1.2 Hz, 1H), 3.81 (s, 3H),
3.71 (s, 3H), 3.49 (d, J = 13.2 Hz, 1H), 3.43 (d, J = 13.2 Hz, 1H),
2.44 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 151.3, 147.1, 146.9,
145.8, 136.6, 135.6, 134.3, 131.0, 129.9, 129.0, 121.6, 111.9,
107.4, 107.1, 100.8, 60.3, 56.0, 40.5, 24.3.
4.4.19.
dibenzo[a,d][7]annulene
8-Isopropoxy-1,2,7-trimethoxy-5H-
(1s) and 7-Isopropoxy-1,2,8-
trimethoxy-5H-dibenzo[a,d][7]annulene (1t). According to the
general procedure, the reaction was performed in two-step
including (i) OsO4 (2.5%, 0.6 mL in THF), NMO (50% in water,
300 mg, 1.3 mmol), NaIO4 (150 mg, 0.7 mmol), and a mixture of
7s and 7t (214 mg, 0.6 mmol) in the cosolvent of THF (6 mL)
4.4.16.
2,3,7,8-Tetramethoxy-5H-dibenzo[a,d][7]annulene
(1p). According to the general procedure, the reaction was
performed in two-step including (i) OsO4 (2.5%, 0.6 mL in THF),
NMO (50% in water, 300 mg, 1.3 mmol), NaIO4 (150 mg, 0.7
mmol) and 7p (205 mg, 0.6 mmol) in the cosolvent of THF (6
mL) and water (6 mL) at 25 oC for 3 h, (ii) BF3·OEt2 (71 mg, 0.5
mmol) and in situ-generated 8p without further purification in
CH2Cl2 (8 mL) at 25 oC for 2 h. Purification on silica gel
(hexanes/EtOAc = 6/1) afforded 1p (95%, 178 mg). Colorless
solid; mp = 197-198 oC (recrystallized from hexanes and EtOAc);
HRMS (ESI, M++Na) calcd for C19H20O4Na 335.1253, found
335.1255; 1H NMR (400 MHz, CDCl3): δ 6.88 (s, 2H), 6.80 (d, J
= 8.4 Hz, 4H), 3.92 (s, 6H), 3.85 (s, 6H), 3.60 (s, 2H); 13C NMR
(100 MHz, CDCl3): δ 149.4 (2x), 147.1 (2x), 130.6 (2x), 129.8
(2x), 127.9 (2x), 111.0 (2x), 110.8 (2x), 55.95 (2x), 55.92 (2x),
40.6. Single-crystal X-ray diagram: crystal of 1p was grown by
slow diffusion of EtOAc into a solution of 1p in CH2Cl2 to yield
colorless prisms. The compound crystallizes in the orthorhombic
crystal system, space group P n m a, a = 10.2063(6) Å, b =
26.4494(15) Å, c = 6.0198(4) Å, V = 1625.05(17) Å3, Z = 4, dcalcd
= 1.277 g/cm3, F(000) = 664, 2θ range 1.54-26.48o, R indices
(all data) R1 = 0.0550, wR2 = 0.1102.
o
and water (6 mL) at 25 C for 3 h, (ii) BF3·OEt2 (71 mg, 0.5
mmol) and in situ-generated 8s and 8t without further
purification in CH2Cl2 (8 mL) at 25 C for 2 h. Purification on
o
silica gel (hexanes/EtOAc = 6/1) afforded a mixture of 1s and 1t
(93%, 190 mg) with a ratio of 2:1. HRMS (ESI, M++Na) calcd
1
for C21H24O4Na 363.1565, found 363.1568; H NMR (400 MHz,
CDCl3): δ 7.28-7.24 (m, 1H), 7.03-6.98 (m, 2H), 6.90-6.82 (m,
3H), 4.60-4.52 (m, 1H), 3.89 (s, 3H), 3.84 (br s, 6H), 3.62 (s, 2H),
1.41-1.35 (m, 6H).
4.4.20.
8-(Benzyloxy)-1,2,7-trimethoxy-5H-
dibenzo[a,d][7]annulene (1u). According to the general
procedure, the reaction was performed in two-step including (i)
OsO4 (2.5%, 0.6 mL in THF), NMO (50% in water, 300 mg, 1.3
mmol), NaIO4 (150 mg, 0.7 mmol) and 7u (243 mg, 0.6 mmol) in
o
the cosolvent of THF (6 mL) and water (6 mL) at 25 C for 3 h,
(ii) BF3·OEt2 (71 mg, 0.5 mmol) and in situ-generated 8u without
further purification in CH2Cl2 (8 mL) at 25 oC for 2 h.
Purification on silica gel (hexanes/EtOAc = 6/1) afforded 1u
o
4.4.17. 2,3,4,7,8-Pentamethoxy-5H-dibenzo[a,d][7]annulene
(1q). According to the general procedure, the reaction was
performed in two-step including (i) OsO4 (2.5%, 0.6 mL in THF),
NMO (50% in water, 300 mg, 1.3 mmol), NaIO4 (150 mg, 0.7
mmol) and 7q (223 mg, 0.6 mmol) in the cosolvent of THF (6
mL) and water (6 mL) at 25 oC for 3 h, (ii) BF3·OEt2 (71 mg, 0.5
mmol) and in situ-generated 8q without further purification in
CH2Cl2 (8 mL) at 25 oC for 2 h. Purification on silica gel
(hexanes/EtOAc = 6/1) afforded 1q (91%, 187 mg). Colorless
solid; mp = 101-102 oC (recrystallized from hexanes and EtOAc);
HRMS (ESI, M++Na) calcd for C20H22O5Na 365.1358, found
365.1362; 1H NMR (400 MHz, CDCl3): δ 6.90 (s, 1H), 6.87 (d, J
= 12.0 Hz, 2H), 6.78 (s, 1H), 6.60 (s, 1H), 3.93 (s, 3H), 3.92 (s,
3H), 3.88 (s, 3H), 3.85 (s, 3H), 3.83 (s, 3H), 3.67 (s, 2H); 13C
NMR (100 MHz, CDCl3): δ 151.1, 149.9, 149.6, 147.1, 142.9,
131.4, 131.1, 130.9, 129.9, 128.2, 124.5, 111.2, 111.0, 106.8,
61.5, 61.0, 56.0 (3x), 31.5.
(44%, 103 mg). Colorless solid; mp = 117-118 C (recrystallized
from hexanes and EtOAc); HRMS (ESI, M++Na) calcd for
C25H24O4Na 411.1565, found 411.1567; 1H NMR (400 MHz,
CDCl3): δ 7.47-7.45 (m, 2H), 7.40-7.31 (m, 3H), 7.25 (d, J = 12.0
Hz, 1H), 7.00 (d, J = 12.0 Hz, 1H), 6.95 (d, J = 8.4 Hz, 1H), 6.86
(d, J = 8.4 Hz, 1H), 6.83 (s, 1H), 6.82 (s, 1H), 5.16 (s, 2H), 3.86
(s, 3H), 3.83 (s, 3H), 3.81 (s, 3H), 3.55 (s, 2H); 13C NMR (100
MHz, CDCl3): δ 150.7, 148.8, 147.8, 146.1, 137.1, 132.8, 129.3,
128.52 (2x), 128.49, 127.8, 127.3 (2x), 127.2, 124.9, 122.6, 113.4,
112.5, 111.8, 71.1, 70.5, 60.7, 56.2, 56.0, 40.4.
4.4.21.
7-(Benzyloxy)-1,2,8-trimethoxy-5H-
dibenzo[a,d][7]annulene (1v). According to the general
procedure, the reaction was performed in two-step including (i)
OsO4 (2.5%, 0.6 mL in THF), NMO (50% in water, 300 mg, 1.3
mmol), NaIO4 (150 mg, 0.7 mmol) and 7v (243 mg, 0.6 mmol) in
o
the cosolvent of THF (6 mL) and water (6 mL) at 25 C for 3 h,
(ii) BF3·OEt2 (71 mg, 0.5 mmol) and in situ-generated 8v without
further purification in CH2Cl2 (8 mL) at 25 oC for 2 h.
Purification on silica gel (hexanes/EtOAc = 6/1) afforded 1v
4.4.18.
7,8-Diisopropoxy-1,2-dimethoxy-5H-
dibenzo[a,d][7]annulene (1r). According to the general
procedure, the reaction was performed in two-step including (i)
OsO4 (2.5%, 0.6 mL in THF), NMO (50% in water, 300 mg, 1.3
mmol), NaIO4 (150 mg, 0.7 mmol) and 7r (231 mg, 0.6 mmol) in
o
(44%, 103 mg). Colorless solid; mp = 121-122 C (recrystallized
from hexanes and EtOAc); HRMS (ESI, M++Na) calcd for
C25H24O4Na 411.1565, found 411.1568; 1H NMR (400 MHz,
CDCl3): δ 7.45-7.27 (m, 5H), 7.22 (d, J = 12.4 Hz, 1H), 6.99 (d, J
= 8.4 Hz, 1H), 6.93 (d, J = 12.0 Hz, 1H), 6.88 (d, J = 8.8 Hz, 1H),
o
the cosolvent of THF (6 mL) and water (6 mL) at 25 C for 3 h,
(ii) BF3·OEt2 (71 mg, 0.5 mmol) and in situ-generated 8r without

4.4.25. 5-Isopropoxy-1,2,3,6-tetramethoxyanthracene (13d).
6.83 (s, 1H), 6.82 (s, 1H), 5.12 (s, 2H), 3.92 (s,A3HC),C3.E83P(Ts,E3HD), MANUSCRIPT
3.81 (s, 3H), 3.60 (s, 2H); 13C NMR (100 MHz, CDCl3): δ 150.7,
150.2, 146.4, 146.0, 137.2, 132.7, 132.1, 131.5, 129.4, 128.5 (2x),
127.8, 127.2 (2x), 124.6, 122.6, 114.0, 112.5, 111.3, 71.3, 70.5,
60.7, 56.1, 56.0, 40.5.
According to the general procedure, the reaction was performed
in two-step including (i) OsO4 (2.5%, 0.6 mL in THF), NMO
(50% in water, 300 mg, 1.3 mmol), NaIO4 (150 mg, 0.7 mmol)
and 11d (232 mg, 0.6 mmol) in the cosolvent of THF (6 mL) and
o
water (6 mL) at 25 C for 3 h, (ii) BF3·OEt2 (71 mg, 0.5 mmol)
4.4.22. 1,2,6,7-Tetramethoxyanthracene (13a). According to
the general procedure, the reaction was performed in two-step
including (i) OsO4 (2.5%, 0.6 mL in THF), NMO (50% in water,
300 mg, 1.3 mmol), NaIO4 (150 mg, 0.7 mmol) and 11a (197 mg,
0.6 mmol) in the cosolvent of THF (6 mL) and water (6 mL) at
and in situ-generated 12d without further purification in CH2Cl2
(8 mL) at 25 oC for 2 h. Purification on silica gel (hexanes/EtOAc
= 6/1) afforded 13d (91%, 195 mg). Colorless gum; HRMS (ESI,
1
M++Na) calcd for C21H24O5Na 379.1514, found 379.1518; H
NMR (400 MHz, CDCl3): δ 8.53 (s, 1H), 8.51 (s, 1H), 7.76 (d, J
= 9.2 Hz, 1H), 7.30 (d, J = 9.2 Hz, 1H), 7.05 (s, 1H), 4.79-4.73
(m, 1H), 4.13 (s, 3H), 4.03 (s, 3H), 4.01 (s, 3H), 4.00 (s, 3H),
1.42 (d, J = 6.4 Hz, 6H); 13C NMR (100 MHz, CDCl3): δ 153.1,
147.1, 147.0, 140.0, 139.6, 129.5, 129.4, 127.6, 124.6, 123.0,
120.1, 118.2, 116.0, 101.0, 75.1, 61.3, 61.2, 57.1, 55.8, 22.8 (2x).
o
25 C for 3 h, (ii) BF3·OEt2 (71 mg, 0.5 mmol) and in situ-
generated 12a without further purification in CH2Cl2 (8 mL) at 25
oC for 2 h. Purification on silica gel (hexanes/EtOAc = 6/1)
o
afforded 13a (93%, 166 mg). Colorless solid; mp = 151-152 C
(recrystallized from hexanes and EtOAc); HRMS (ESI, M++Na)
1
calcd for C18H18O4Na 321.1097, found 321.1108; H NMR (400
MHz, CDCl3): δ 8.48 (s, 1H), 8.14 (s, 1H), 7.68 (d, J = 9.2 Hz,
1H), 7.27 (d, J = 9.2 Hz, 1H), 7.22 (s, 1H), 7.12 (s, 1H), 4.08 (s,
3H), 4.03 (s, 3H), 4.01 (br s, 6H); 13C NMR (100 MHz, CDCl3):
δ 150.1, 149.6, 146.3, 141.9, 128.8, 128.0, 127.3, 126.8, 124.1,
123.9, 117.2, 115.8, 104.9, 104.6, 60.9, 57.2, 55.70, 55.68.
Single-crystal X-ray diagram: crystal of 13a was grown by slow
diffusion of EtOAc into a solution of 13a in CH2Cl2 to yield
colorless prisms. The compound crystallizes in the triclinic
crystal system, space group P -1, a = 6.8802(3) Å, b = 12.3630(6)
Å, c = 18.9082(9) Å, V = 1518.82(12) Å3, Z = 4, dcalcd = 1.305
g/cm3, F(000) = 632, 2θ range 1.14-26.39o, R indices (all data)
R1 = 0.0791, wR2 = 0.1623.
4.4.26.
5-Butoxy-1,2,3,6-tetramethoxyanthracene
(13e).
According to the general procedure, the reaction was performed
in two-step including (i) OsO4 (2.5%, 0.6 mL in THF), NMO
(50% in water, 300 mg, 1.3 mmol), NaIO4 (150 mg, 0.7 mmol)
and 11e (240 mg, 0.6 mmol) in the cosolvent of THF (6 mL) and
o
water (6 mL) at 25 C for 3 h, (ii) BF3·OEt2 (71 mg, 0.5 mmol)
and in situ-generated 12e without further purification in CH2Cl2
(8 mL) at 25 oC for 2 h. Purification on silica gel (hexanes/EtOAc
= 6/1) afforded 13e (87%, 193 mg). Colorless solid; mp = 45-46
oC (recrystallized from hexanes and EtOAc); HRMS (ESI,
M++Na) calcd for C22H26O5Na 393.1670, found 393.1673; H
1
NMR (400 MHz, CDCl3): δ 8.55 (s, 1H), 8.50 (s, 1H), 7.76 (d, J
= 9.2 Hz, 1H), 7.29 (d, J = 9.2 Hz, 1H), 7.06 (s, 1H), 4.21 (t, J =
6.4 Hz, 2H), 4.14 (s, 3H), 4.03 (s, 3H), 4.02 (s, 3H), 4.01 (s, 3H),
1.99-1.92 (m, 2H), 1.70-1.61 (m, 2H), 1.06 (t, J = 7.6 Hz, 3H);
13C NMR (100 MHz, CDCl3): δ 153.1, 147.0, 146.9, 141.1, 140.0,
129.6, 128.4, 127.6, 124.7, 123.1, 120.3, 117.5, 116.2, 101.0,
73.2, 61.3, 61.2, 57.3, 55.7, 32.5, 19.3, 13.9.
4.4.23. 1,2,3,5,6-Pentamethoxyanthracene (13b). According to
the general procedure, the reaction was performed in two-step
including (i) OsO4 (2.5%, 0.6 mL in THF), NMO (50% in water,
300 mg, 1.3 mmol), NaIO4 (150 mg, 0.7 mmol) and 11b (215 mg,
0.6 mmol) in the cosolvent of THF (6 mL) and water (6 mL) at
o
25 C for 3 h, (ii) BF3·OEt2 (71 mg, 0.5 mmol) and in situ-
4.5. A representative synthetic procedure of skeleton 14 is as
follows:
generated 12b without further purification in CH2Cl2 (8 mL) at
o
25 C for 2 h. Purification on silica gel (hexanes/EtOAc = 6/1)
o
afforded 13b (95%, 187 mg). Colorless solid; mp = 109-110 C
BF3·OEt2 (71 mg, 0.5 mmol) was added to a solution of 5a-5f,
10a (1.0 mmol) and 6a, 6c-6g (0.6 mmol) in CH2Cl2 (6 mL) at 25
oC. The reaction mixture was stirred at 25 oC for 3 h. The
reaction mixture was concentrated and the residue was diluted
with water (10 mL) and the mixture was extracted with CH2Cl2
(3 x 20 mL). The combined organic layers were washed with
brine, dried, filtered and evaporated to afford crude product under
reduced pressure. Purification on silica gel (hexanes/EtOAc =
3/1) afforded 14a-14o.
(recrystallized from hexanes and EtOAc); HRMS (ESI, M++Na)
1
calcd for C19H20O5Na 351.1202, found 351.1204; H NMR (400
MHz, CDCl3): δ 8.55 (s, 1H), 8.48 (s, 1H), 7.78 (d, J = 9.2 Hz,
1H), 7.30 (d, J = 9.2 Hz, 1H), 7.06 (s, 1H), 4.13 (s, 3H), 4.07 (s,
3H), 4.03 (s, 3H), 4.02 (s, 3H), 4.01 (s, 3H); 13C NMR (100 MHz,
CDCl3): δ 153.2, 147.0, 146.9, 141.6, 140.1, 129.7, 127.8, 127.5,
125.1, 123.1, 120.4, 117.3, 115.8, 100.9, 61.3, 61.2, 61.0, 57.2,
55.8.
4.4.24.
1-Isopropoxy-2,6,7-trimethoxyanthracene
(13c).
4.5.1.
4,4'-((4,5-Dimethoxy-1,2-
According to the general procedure, the reaction was performed
in two-step including (i) OsO4 (2.5%, 0.6 mL in THF), NMO
(50% in water, 300 mg, 1.3 mmol), NaIO4 (150 mg, 0.7 mmol)
and 11c (214 mg, 0.6 mmol) in the cosolvent of THF (6 mL) and
phenylene)bis(methylene))bis(3-allyl-1,2-dimethoxybenzene)
(14a). According to the general procedure, the reaction was
performed in the presence of BF3·OEt2 (71 mg, 0.5 mmol), 5a
(208 mg, 1.0 mmol) and 6a (83 mg, 0.6 mmol) in CH2Cl2 (6 mL)
at 25 oC for 3 h. Purification on silica gel (hexanes/EtOAc = 3/1)
o
water (6 mL) at 25 C for 3 h, (ii) BF3·OEt2 (71 mg, 0.5 mmol)
o
and in situ-generated 12c without further purification in CH2Cl2
(8 mL) at 25 oC for 2 h. Purification on silica gel (hexanes/EtOAc
= 6/1) afforded 13c (86%, 168 mg). Colorless solid; mp = 63-64
oC (recrystallized from hexanes and EtOAc); HRMS (ESI,
afforded 14a (95%, 246 mg). Colorless solid; mp = 104-105 C
(recrystallized from hexanes and EtOAc); HRMS (ESI, M++Na)
1
calcd for C32H38O6Na 541.2555, found 541.2556; H NMR (400
MHz, CDCl3): δ 6.71 (d, J = 8.4 Hz, 2H), 6.58 (d, J = 8.4 Hz,
2H), 6.51 (s, 2H), 5.89-5.80 (m, 2H), 4.91 (dq, J = 1.6, 10.0 Hz,
2H), 4.82 (dq, J = 1.6, 17.2 Hz, 2H), 3.83 (s, 6H), 3.81 (s, 6H),
3.76 (s, 4H), 3.74 (s, 6H), 3.36 (dt, J = 1.6, 6.0 Hz, 4H); 13C
NMR (100 MHz, CDCl3): δ 150.9 (2x), 147.2 (2x), 147.1 (2x),
136.4 (2x), 131.8 (2x), 131.7 (2x), 130.8 (2x), 124.2 (2x), 114.7
(2x), 113.3 (2x), 110.0 (2x), 60.6 (2x), 55.7 (2x), 55.4 (2x), 34.7
(2x), 30.4 (2x). Single-crystal X-ray diagram: crystal of 14a was
1
M++Na) calcd for C20H22O4Na 349.1409, found 349.1410; H
NMR (400 MHz, CDCl3): δ 8.50 (s, 1H), 8.14 (s, 1H), 7.67 (d, J
= 9.2 Hz, 1H), 7.28 (d, J = 8.8 Hz, 1H), 7.22 (s, 1H), 7.14 (s, 1H),
4.80-4.74 (m, 1H), 4.05 (s, 3H), 4.02 (s, 3H), 3.99 (s, 3H), 1.43
(d, J = 6.4 Hz, 6H); 13C NMR (100 MHz, CDCl3): δ 150.1, 149.7,
146.6, 140.0, 128.7, 128.4, 128.2, 127.3, 123.71, 123.65, 118.2,
116.3, 105.2, 104.7, 75.1, 57.3, 55.81, 55.78, 22.8 (2x).

14
Tetrahedron
grown by slow diffusion of EtOAc into a solution of 14a in
silica gel (hexanes/EtOAc = 3/1) afforded 14e (83%, 244 mg).
ACCEPTED MANUSCRIPT
CH2Cl2 to yield colorless prisms. The compound crystallizes in
the triclinic crystal system, space group P -1, a = 8.4191(8) Å, b
= 10.7663(10) Å, c = 15.3786(14) Å, V = 1348.2(2) Å3, Z = 2,
dcalcd = 1.278 g/cm3, F(000) = 556, 2θ range 1.36-27.29o, R
indices (all data) R1 = 0.1167, wR2 = 0.2450.
Colorless gum; HRMS (ESI, M++Na) calcd for C37H46O6Na
1
609.3179, found 609.3181; H NMR (400 MHz, CDCl3): δ 6.72
(d, J = 8.4 Hz, 2H), 6.60 (d, J = 8.4 Hz, 2H), 6.42 (s, 2H), 5.89-
5.80 (m, 2H), 5.88 (s, 2H), 4.90 (dq, J = 1.6, 10.0 Hz, 2H), 4.80
(dq, J = 1.6, 17.2 Hz, 2H), 3.94 (t, 6.4 Hz, 4H), 3.83 (s, 6H), 3.74
(s, 4H), 3.34 (dt, J = 5.6 Hz, 4H), 1.80-1.73 (m, 4H), 1.53-1.48
(m, 4H), 0.98 (t, J = 7.6 Hz, 6H); 13C NMR (100 MHz, CDCl3): δ
151.3 (2x), 146.8 (2x), 145.8 (2x), 136.6 (2x), 132.2 (2x), 132.1
(2x), 131.6 (2x), 124.4 (2x), 114.7 (2x), 110.2 (2x), 109.8 (2x),
100.6, 72.9 (2x), 55.6 (2x), 35.0 (2x), 32.4 (2x), 30.7 (2x), 19.2
(2x), 13.9 (2x).
4.5.2.
5,6-Bis(2-allyl-3,4-
dimethoxybenzyl)benzo[d][1,3]dioxole (14b). According to the
general procedure, the reaction was performed in the presence of
BF3·OEt2 (71 mg, 0.5 mmol), 5a (208 mg, 1.0 mmol) and 6c (73
mg, 0.6 mmol) in CH2Cl2 (6 mL) at 25 oC for 3 h. Purification on
silica gel (hexanes/EtOAc = 3/1) afforded 14b (89%, 224 mg).
Colorless gum; HRMS (ESI, M++Na) calcd for C31H34O6Na
4.5.6.
4,4'-((4,5-Dimethoxy-1,2-
1
525.2243, found 525.2245; H NMR (400 MHz, CDCl3): δ 6.74
phenylene)bis(methylene))bis(3-allyl-2-(cyclopentyloxy)-1-
methoxybenzene) (14f). According to the general procedure, the
reaction was performed in the presence of BF3·OEt2 (71 mg, 0.5
mmol), 5d (262 mg, 1.0 mmol) and 6a (83 mg, 0.6 mmol) in
CH2Cl2 (6 mL) at 25 oC for 3 h. Purification on silica gel
(hexanes/EtOAc = 3/1) afforded 14f (90%, 282 mg). Colorless
gum; HRMS (ESI, M++Na) calcd for C40H50O6Na 649.3491,
(d, J = 8.4 Hz, 2H), 6.63 (d, J = 8.4 Hz, 2H), 6.44 (s, 2H), 5.90-
5.82 (m, 2H), 5.88 (s, 2H), 4.93 (dq, J = 1.6, 10.0 Hz, 2H), 4.82
(dq, J = 1.6, 17.2 Hz, 2H), 3.85 (s, 6H), 3.82 (s, 6H), 3.75 (s, 4H),
3.34 (dt, J = 1.6, 5.6 Hz, 4H); 13C NMR (100 MHz, CDCl3): δ
151.2 (2x), 147.5 (2x), 145.8 (2x), 136.6 (2x), 132.1 (2x), 132.0
(2x), 131.6 (2x), 124.6 (2x), 114.8 (2x), 110.2 (2x), 109.8 (2x),
100.6, 60.8 (2x), 55.6 (2x), 35.0 (2x), 30.5 (2x).
1
found 649.3492; H NMR (400 MHz, CDCl3): δ 6.70 (d, J = 8.8
Hz, 2H), 6.56 (d, J = 8.8 Hz, 2H), 6.47 (s, 2H), 5.86-5.76 (m, 2H),
4.90-4.78 (m, 6H), 3.81 (s, 6H), 3.76 (s, 4H), 3.72 (s, 6H), 3.34
(d, J = 5.6 Hz, 4H), 1.90-1.78 (m, 8H), 1.75-1.69 (m, 4H), 1.62-
1.54 (m, 4H); 13C NMR (100 MHz, CDCl3): δ 151.0 (2x), 147.0
(2x), 145.3 (2x), 136.3 (2x), 132.4 (2x), 131.9 (2x), 131.1 (2x),
123.9 (2x), 114.7 (2x), 113.1 (2x), 110.2 (2x), 84.1 (2x), 55.7
(2x), 55.5 (2x), 35.0 (2x), 32.7 (4x), 30.9 (2x), 23.7 (4x).
4.5.3.
4,4'-((4,5-Dimethoxy-1,2-
phenylene)bis(methylene))bis(3-allyl-2-isopropoxy-1-
methoxybenzene) (14c). According to the general procedure, the
reaction was performed in the presence of BF3·OEt2 (71 mg, 0.5
mmol), 5b (236 mg, 1.0 mmol) and 6a (83 mg, 0.6 mmol) in
CH2Cl2 (6 mL) at 25 oC for 3 h. Purification on silica gel
(hexanes/EtOAc = 3/1) afforded 14c (91%, 262 mg). Colorless
gum; HRMS (ESI, M++Na) calcd for C36H46O6Na 597.3179,
4.5.7.
4,4'-((4,5-Dimethoxy-1,2-
1
found 597.3182; H NMR (400 MHz, CDCl3): δ 6.69 (d, J = 8.4
phenylene)bis(methylene))bis(3-(but-3-en-2-yl)-1,2-
Hz, 2H), 6.56 (d, J = 8.4 Hz, 2H), 6.47 (s, 2H), 5.86-5.76 (m, 2H),
4.89 (dq, J = 1.6, 10.0 Hz, 2H), 4.81 (dq, J = 2.0, 17.2 Hz, 2H),
4.57-4.51 (m, 2H), 3.81 (s, 6H), 3.76 (s, 4H), 3.72 (s, 6H), 3.38
(dt, J = 1.6, 6.0 Hz, 4H), 1.27 (d, J = 6.4 Hz, 12H); 13C NMR
(100 MHz, CDCl3): δ 151.2 (2x), 147.1 (2x), 145.0 (2x), 136.4
(2x), 133.0 (2x), 131.9 (2x), 131.2 (2x), 124.0 (2x), 114.8 (2x),
113.1 (2x), 110.0 (2x), 74.3 (2x), 55.7 (2x), 55.5 (2x), 35.0 (2x),
31.1 (2x), 22.5 (4x).
dimethoxybenzene) (14g). According to the general procedure,
the reaction was performed in the presence of BF3·OEt2 (71 mg,
0.5 mmol), 5e (222 mg, 1.0 mmol) and 6a (83 mg, 0.6 mmol) in
CH2Cl2 (6 mL) at 25 oC for 3 h. Purification on silica gel
(hexanes/EtOAc = 3/1) afforded 14g (92%, 251 mg). Colorless
o
solid; mp = 99-100 C (recrystallized from hexanes and EtOAc);
HRMS (ESI, M++Na) calcd for C34H42O6Na 569.2867, found
1
569.2869; H NMR (400 MHz, CDCl3): δ 6.71 (d, J = 8.4 Hz,
2H), 6.63 (d, J = 8.4 Hz, 2H), 6.44 (d, J = 2.4 Hz, 2H), 6.17-6.08
(m, 2H), 4.90 (dq, J = 1.6, 10.0 Hz, 2H), 4.82-4.77 (m, 2H), 3.91-
3.74 (m, 6H), 3.84 (s, 6H), 3.81 (s, 6H), 3.70 (s, 6H), 1.31 (d, J =
7.2 Hz, 3H), 1.30 (d, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): δ 151.6 (2x), 147.9 (2x), 147.0 (2x), 142.8 (2x), 137.79,
137.77, 131.1 (2x), 130.7 (2x), 125.24 (2x), 125.20 (2x), 113.4,
113.3, 112.7 (2x), 110.1 (2x), 60.6 (2x), 55.8 (2x), 55.5 (2x), 35.8
(2x), 18.8 (2x).
4.5.4.
4,4'-((4,5-Dimethoxy-1,2-
phenylene)bis(methylene))bis(3-allyl-2-butoxy-1-
methoxybenzene) (14d). According to the general procedure, the
reaction was performed in the presence of BF3·OEt2 (71 mg, 0.5
mmol), 5c (250 mg, 1.0 mmol) and 6a (83 mg, 0.6 mmol) in
CH2Cl2 (6 mL) at 25 oC for 3 h. Purification on silica gel
(hexanes/EtOAc = 3/1) afforded 14d (92%, 277 mg). Colorless
gum; HRMS (ESI, M++Na) calcd for C38H50O6Na 625.3491,
1
found 625.3493; H NMR (400 MHz, CDCl3): δ 6.70 (d, J = 8.4
4.5.8.
5,6-Bis(2-(but-3-en-2-yl)-3,4-
Hz, 2H), 6.57 (d, J = 8.4 Hz, 2H), 6.49 (s, 2H), 5.89-5.79 (m, 2H),
4.90 (dq, J = 1.6, 10.0 Hz, 2H), 4.81 (dq, J = 1.6, 17.2 Hz, 2H),
3.93 (t, J = 6.8 Hz, 4H), 3.82 (s, 6H), 3.76 (s, 4H), 3.73 (s, 6H),
3.36 (d, J = 5.6 Hz, 4H), 1.80-1.73 (m, 4H), 1.55-1.46 (m, 4H),
0.97 (t, J = 7.2 Hz, 6H); 13C NMR (100 MHz, CDCl3): δ 151.1
(2x), 147.1 (2x), 146.6 (2x), 136.6 (2x), 132.0 (2x), 131.8 (2x),
131.0 (2x), 124.2 (2x), 114.7 (2x), 113.2 (2x), 110.0 (2x), 72.8
(2x), 55.7 (2x), 55.5 (2x), 34.8 (2x), 32.3 (2x), 30.6 (2x), 19.1
(2x), 13.9 (2x).
dimethoxybenzyl)benzo[d][1,3]dioxole (14h). According to the
general procedure, the reaction was performed in the presence of
BF3·OEt2 (71 mg, 0.5 mmol), 5e (222 mg, 1.0 mmol) and 6c (73
mg, 0.6 mmol) in CH2Cl2 (6 mL) at 25 oC for 3 h. Purification on
silica gel (hexanes/EtOAc = 3/1) afforded 14h (85%, 226 mg).
Colorless gum; HRMS (ESI, M++Na) calcd for C33H38O6Na
1
553.2555, found 553.2556; H NMR (400 MHz, CDCl3): δ 7.06
(d, J = 8.4 Hz, 2H), 6.76 (d, J = 8.4 Hz, 2H), 6.41 (s, 2H), 6.25-
6.16 (m, 2H), 5.87 (s, 2H), 5.04-4.98 (m, 4H), 4.52 (d, J = 12.0
Hz, 2H), 4.76 (d, J = 12.0 Hz, 2H), 4.03-3.94 (m, 2H), 3.85 (s,
6H), 3.80 (s, 6H), 1.43 (d, J = 7.2 Hz, 6H); 13C NMR (100 MHz,
CDCl3): δ 152.8 (2x), 147.7 (2x), 143.2 (2x), 138.3 (2x), 132.3
(2x), 128.9 (2x), 125.6 (2x), 119.1 (2x), 112.6 (2x), 110.2 (2x),
4.5.5.
5,6-Bis(2-allyl-3-butoxy-4-
methoxybenzyl)benzo[d][1,3]dioxole (14e). According to the
general procedure, the reaction was performed in the presence of
BF3·OEt2 (71 mg, 0.5 mmol), 5c (250 mg, 1.0 mmol) and 6c (73
mg, 0.6 mmol) in CH2Cl2 (6 mL) at 25 oC for 3 h. Purification on

1
calcd for C38H42O6Na 617.2867, found 617.2869; H NMR (400
109.9 (2x), 100.6, 70.3 (2x), 60.6 (2x), 55.6 (2Ax),C36C.5E(P2xT),E19D.2 MANUSCRIPT
(2x).
MHz, CDCl3): δ 7.34-7.25 (m, 4H), 6.72 (d, J = 8.4 Hz, 1H), 6.70
(d, J = 8.4 Hz, 1H), 6.58 (d, J = 8.4 Hz, 1H), 6.55 (d, J = 8.4 Hz,
1H), 6.53 (s, 1H), 6.49 (s, 1H), 5.91-5.74 (m, 2H), 5.01 (s, 2H),
5.94.94 (dq, J = 1.6, 10.0 Hz, 1H), 4.89 (dq, J = 1.6, 10.0 Hz,
1H), 4.86 (dq, J = 2.0, 17.2 Hz, 1H), 4.77 (dq, J = 1.6, 17.2 Hz,
1H), 3.87 (s, 3H), 3.85 (s, 3H), 3.82 (s, 3H), 3.81 (s, 3H), 3.77 (s,
2H), 3.76 (s, 3H), 3.69 (s, 3H), 3.38 (dt, J = 1.6, 6.0 Hz, 2H),
3.27 (dt, J = 1.6, 6.0 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ
151.0 (2x), 147.8, 147.34, 147.32, 146.2, 137.2, 136.6, 136.5,
132.0, 131.9, 131.7, 131.6, 131.4, 131.1, 128.3 (2x), 127.6, 127.4
(2x), 124.7, 124.3, 116.0, 114.8, 114.7, 113.9, 111.0, 110.1, 71.0,
60.8 (2x), 56.0, 55.57, 55.55, 34.8, 34.6, 30.50, 30.46.
4.5.9.
5,5'-((4,5-Dimethoxy-1,2-
phenylene)bis(methylene))bis(4-but-2-en-1-yl)-1,2-
dimethoxybenzene) (14i). According to the general procedure,
the reaction was performed in the presence of BF3·OEt2 (71 mg,
0.5 mmol), 5f (222 mg, 1.0 mmol) and 6a (83 mg, 0.6 mmol) in
CH2Cl2 (6 mL) at 25 oC for 3 h. Purification on silica gel
(hexanes/EtOAc = 3/1) afforded 14i (95%, 260 mg). Colorless
o
solid; mp = 90-91 C (recrystallized from hexanes and EtOAc);
HRMS (ESI, M++Na) calcd for C34H42O6Na 569.2867, found
1
569.2868; H NMR (400 MHz, CDCl3): δ 6.69 (s, 2H), 6.47 (s,
2H), 6.44 (s, 2H), 5.48-5.41 (m, 2H), 5.35-5.28 (m, 2H), 3.85 (s,
6H), 3.78 (s, 4H), 3.71 (s, 6H), 3.69 (s, 6H), 3.14 (d, J = 6.4 Hz,
4H), 1.59 (d, J = 1.2, 6.4 Hz, 6H); 13C NMR (100 MHz, CDCl3):
δ 147.1 (2x), 147.0 (2x), 146.9 (2x), 131.0 (2x), 130.8 (2x), 129.9
(2x), 129.3 (2x), 125.8 (2x), 112.9 (2x), 112.7 (4x), 55.7 (2x),
55.6 (4x), 35.6 (2x), 34.8 (2x), 17.6 (2x).
4.5.13.
4,4'-((4,5-Dimethoxy-1,2-
phenylene)bis(methylene))bis(1,2-dimethoxy-3-prop-1-en-1-
ylbenzene) (14m). According to the general procedure, the
reaction was performed in the presence of BF3·OEt2 (71 mg, 0.5
mmol), 10a (208 mg, 1.0 mmol) and 6a (83 mg, 0.6 mmol) in
CH2Cl2 (6 mL) at 25 oC for 3 h. Purification on silica gel
(hexanes/EtOAc = 3/1) afforded 14m (88%, 228 mg). Colorless
solid; mp = 100-101 oC (recrystallized from hexanes and EtOAc);
HRMS (ESI, M++Na) calcd for C32H38O6Na 541.2555, found
4.5.10.
4,4'-((4,5-Diisopropoxy-1,2-
phenylene)bis(methylene))bis(3-allyl-1,2-dimethoxybenzene)
(14j). According to the general procedure, the reaction was
performed in the presence of BF3·OEt2 (71 mg, 0.5 mmol), 5a
(208 mg, 1.0 mmol) and 6d (117 mg, 0.6 mmol) in CH2Cl2 (6
mL) at 25 oC for 3 h. Purification on silica gel (hexanes/EtOAc =
3/1) afforded 14j (92%, 264 mg). Colorless gum; HRMS (ESI,
1
541.2558; H NMR (400 MHz, CDCl3): δ 6.68 (d, J = 8.8 Hz,
2H), 6.59 (d, J = 8.8 Hz, 2H), 6.53 (s, 2H), 6.30 (dq, J = 1.6, 16.0
Hz, 2H), 6.04 (dq, J = 6.4, 16.0 Hz, 2H), 3.83 (s, 6H), 3.81 (s,
4H), 3.75 (s, 6H), 3.74 (s, 6H), 1.84 (dd, J = 1.6, 6.4 Hz, 6H); 13
C
1
M++Na) calcd for C36H46O6Na 597.3179, found 597.3180; H
NMR (100 MHz, CDCl3): δ 151.0 (2x), 147.0 (2x), 146.8 (2x),
131.9 (2x), 131.3 (2x), 131.2 (2x), 131.1 (2x), 124.6 (2x), 124.2
(2x), 113.4 (2x), 110.3 (2x), 59.9 (2x), 55.8 (2x), 55.7 (2x), 35.8
(2x), 19.3 (2x). Single-crystal X-ray diagram: crystal of 14m was
grown by slow diffusion of EtOAc into a solution of 14m in
CH2Cl2 to yield colorless prisms. The compound crystallizes in
the triclinic crystal system, space group C 2/c, a = 26.873(11) Å,
NMR (400 MHz, CDCl3): δ 6.71 (d, J = 8.4 Hz, 2H), 6.60 (d, J =
8.4 Hz, 2H), 6.49 (s, 2H), 5.86-5.77 (m, 2H), 4.89 (dq, J = 1.6,
10.4 Hz, 2H), 4.80 (dq, J = 1.6, 17.2 Hz, 2H), 4.34-4.28 (m, 2H),
3.84 (s, 6H), 3.80 (s, 6H), 3.71 (s, 4H), 3.32 (dt, J = 1.6, 4.4 Hz,
4H), 1.24 (d, J = 6.0 Hz, 12H); 13C NMR (100 MHz, CDCl3): δ
151.1 (2x), 147.4 (2x), 147.2 (2x), 136.6 (2x), 132.14 (2x),
132.09 (2x), 131.8 (2x), 124.6 (2x), 120.2 (2x), 114.8 (2x), 110.2
(2x), 72.1 (2x), 60.8 (2x), 55.6 (2x), 34.8 (2x), 30.6 (2x), 22.2
(4x).
b = 8.423(3) Å, c = 13.594(6) Å, V = 2864(2) Å3, Z = 4, dcalcd
=
1.203 g/cm3, F(000) = 1112, 2θ range 1.63-25.55o, R indices (all
data) R1 = 0.0984, wR2 = 0.1249.
4.5.11.
4,4'-((4-Isopropoxy-5-methoxy-1,2-
4.5.14.
4,4'-((4,6-Dimethoxy-1,3-
phenylene)bis(methylene))bis(3-allyl-1,2-dimethoxybenzene)
(14k). According to the general procedure, the reaction was
performed in the presence of BF3·OEt2 (71 mg, 0.5 mmol), 5a
(208 mg, 1.0 mmol) and 6e (100 mg, 0.6 mmol) in CH2Cl2 (6
mL) at 25 oC for 3 h. Purification on silica gel (hexanes/EtOAc =
3/1) afforded 14k (94%, 257 mg). Colorless solid; mp = 78-79 oC
(recrystallized from hexanes and EtOAc); HRMS (ESI, M++Na)
phenylene)bis(methylene))bis(3-allyl-1,2-dimethoxybenzene)
(14n). According to the general procedure, the reaction was
performed in the presence of BF3·OEt2 (71 mg, 0.5 mmol), 5a
(208 mg, 1.0 mmol) and 6g (83 mg, 0.6 mmol) in CH2Cl2 (6 mL)
at 25 oC for 3 h. Purification on silica gel (hexanes/EtOAc = 3/1)
afforded 14n (95%, 246 mg). Colorless gum; HRMS (ESI,
M++Na) calcd for C32H38O6Na 541.2555, found 541.2556; H
1
1
calcd for C34H42O6Na 569.2867, found 569.2868; H NMR (400
NMR (400 MHz, CDCl3): δ 6.69 (dd, J = 8.4, 11.6 Hz, 4H), 6.51
(s, 1H), 6.48 (s, 1H), 5.97-5.87 (m, 2H), 4.98 (dq, J = 1.6, 10.0
Hz, 2H), 4.93 (dq, J = 1.6, 16.8 Hz, 2H), 3.85 (s, 12H), 3.81 (s,
6H), 3.80 (s, 4H), 3.41 (dt, J = 1.6, 5.6 Hz, 4H); 13C NMR (100
MHz, CDCl3): δ 156.4 (2x), 150.7 (2x), 147.2 (2x), 136.9 (2x),
132.4 (2x), 131.9 (2x), 131.5 (2x), 124.7 (2x), 120.6, 114.6 (2x),
110.0 (2x), 95.1, 60.6 (2x), 55.6 (2x), 55.5 (2x), 31.2 (2x), 30.4
(2x).
MHz, CDCl3): δ 6.72 (d, J = 8.4 Hz, 2H), 6.61 (d, J = 8.4 Hz,
1H), 6.60 (d, J = 8.4 Hz, 1H), 6.51 (s, 1H), 6.50 (s, 1H), 5.90-
5.78 (m, 2H), 4.93-4.89 (m, 2H), 4.85-4.79 (m, 2H), 4.38-4.32
(m, 1H), 3.84 (br s, 6H), 3.82 (s, 3H), 3.81 (s, 3H), 3.76 (s, 2H),
3.73 (s, 2H), 3.72 (s, 3H), 3.37-3.33 (m, 4H), 1.28 (d, J = 6.0 Hz,
6H); 13C NMR (100 MHz, CDCl3): δ 151.0 (2x), 148.6, 147.3,
147.2, 145.2, 136.5 (2x), 131.9, 131.8, 131.7, 131.4, 130.9, 124.5
(2x), 124.3 (2x), 118.0, 114.73, 114.70, 114.0, 110.04, 109.99,
71.2, 60.7, 55.9, 55.49, 55.47, 34.8, 34.6, 30.5, 30.4, 21.9 (2x).
4.5.15.
4,4'-((4,6-Dimethoxy-1,3-
phenylene)bis(methylene))bis(3-(but-3-en-2-yl)-1,2-
4.5.12.
4,4'-((4-(Benzyloxy)-5-methoxy-1,2-
dimethoxybenzene) (14o). According to the general procedure,
the reaction was performed in the presence of BF3·OEt2 (71 mg,
0.5 mmol), 5e (222 mg, 1.0 mmol) and 6g (83 mg, 0.6 mmol) in
CH2Cl2 (6 mL) at 25 oC for 3 h. Purification on silica gel
(hexanes/EtOAc = 3/1) afforded 14o (94%, 257 mg). Colorless
gum; HRMS (ESI, M++Na) calcd for C34H42O6Na 569.2867,
phenylene)bis(methylene))bis(3-allyl-1,2-dimethoxybenzene)
(14l). According to the general procedure, the reaction was
performed in the presence of BF3·OEt2 (71 mg, 0.5 mmol), 5a
(208 mg, 1.0 mmol) and 6f (129 mg, 0.6 mmol) in CH2Cl2 (6
mL) at 25 oC for 3 h. Purification on silica gel (hexanes/EtOAc =
3/1) afforded 14l (91%, 271 mg). Colorless solid; mp = 79-80 oC
(recrystallized from hexanes and EtOAc); HRMS (ESI, M++Na)
1
found 569.2868; H NMR (400 MHz, CDCl3): δ 6.63 (br s, 4H),
6.48 (s, 1H), 6.31 (s, 1H), 6.09-6.00 (m, 2H), 4.89-4.81 (m, 4H),

16
Tetrahedron
(6) (a) Furstner, A.; Thiel, O. R. J. Org. Chem. 2000, 65, 1738-1742. (b)
3.84 (s, 6H), 3.80 (s, 6H), 3.79-3.76 (m, 6H), 3.75 (s, 6H),
ACCEPTED MANUSCRIPT
1.23 (d, J = 7.2 Hz, 6H); 13C NMR (100 MHz, CDCl3): δ 156.0
(2x), 151.3 (2x), 147.8 (2x), 143.3 (2x), 137.7 (2x), 131.5 (2x),
131.4 (2x), 125.6 (2x), 121.1, 112.2 (2x), 110.1 (2x), 94.9, 60.5
(2x), 55.7 (2x), 55.5 (2x), 36.8 (2x), 32.0 (2x), 18.7 (2x).
Michaut, A.; Rodriguez, J. Angew. Chem., Int. Ed. 2006, 45, 5740-5750.
(c) Arican, D.; Bruckner, R. Org. Lett. 2013, 15, 2582-2585.
(7) (a) Tietze, L. F.; Hungerland, T.; Depken, C.; Maab, C.; Stalkeb, D.
Synlett 2012, 23, 2516-2520. (b) Julia-Hernandez, F.; Ziadi, A.;
Nishimura, A.; Martin, R. Angew. Chem., Int. Ed. 2015, 54, 9537-9541.
(c) Fu, X.-F.; Xiang, Y.; Yu, Z.-X. Chem. Eur. J. 2015, 21, 4242-4246.
(8) (a) Wender, P. A.; Takahashi, H.; Witulski, B. J. Am. Chem. Soc. 1995,
117, 4720-4721. (b) Murakami, M.; Kadowaki, S.; Fujimoto, A.;
Ishibashi, M.; Matsuda, T. Org. Lett. 2005, 7, 2059-2061. (c) Bai, Y.;
Tao, W.; Ren, J.; Wang, Z. Angew. Chem., Int. Ed. 2012, 51, 4112-
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2015, 17, 218-221.
Acknowledgments
We thank for the Ministry of Science and Technology of the
Republic of China for financial support (MOST 105-2113-M-
037-001).
(9) (a) Watson, I. D. G.; Ritter, S.; Toste, F. D. J. Am. Chem. Soc. 2009,
131, 2056-2057. (b) Iwai, T.; Okochi, H.; Ito, H.; Sawamura, M. Angew.
Chem., Int. Ed. 2013, 52, 4239-4242. (c) Guelen, S.; Blazejak, M.;
Mouries-Mansuy, V.; Fensterbank, L. Synthesis 2016, 48, 3199-3206.
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M.; Dyker, G. Chem. Commun. 2006, 2260-2261. (b) Beletskiy, E. V.;
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paper. This data can be obtained free of charge via
www.ccdc.cam.ac.uk/conts/retrieving.html ( or from the CCDC, 12
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Supplementary Material
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Scanned photocopies of spectral data and crystallographic data of
compounds 1l, 1p, 13a, 14a and 14m were supported.
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