Trifluoromethanesulfonic acid catalyzed Friedel-Crafts alkylations of 1,2,4-trimethoxybenzene with aldehydes or benzylic alcohols

Article abstract of DOI:10.1021/ol400972m

Trifluoromethanesulfonic acid in acetonitrile was found to efficiently catalyze Friedel-Crafts alkylations of 1,2,4-trimethoxybenzene with a variety of simple or functionalized aldehydes to provide di- or triarylmethanes in high yields. The operationally

Full text of DOI:10.1021/ol400972m

Supporting Information
for
Trifluoromethanesulfonic Acid Catalyzed Friedel-Crafts
Alkylation of 1,2,4-Trimethoxybenzene with Aldehydes or
Benzylic Alcohols
Michael Wilsdorf, Daniel Leichnitz and Hans-Ulrich Reissig*
Institut für Chemie und Biochemie, Freie Universität Berlin
Takustr. 3, D-14195 Berlin, Germany
*
Corresponding author
hreissig@chemie.fu-berlin.de
General Methods, Experimental Procedures, Characterization Data
1
13
H-NMR and C-NMR Spectra of Synthesized Compounds

General Methods
Reactions were, in general, performed at normal atmosphere in a round bottom flask and were sealed with
a cap after additon of substrates, solvent and acid. Acetonitrile was purchased from Sigma Aldrich
®
(
CHROMASOLV Plus for HPLC, >99.9%). Trifluoromethansulfonic acid was purchased from Merck. All
other reagents were purchased from commercial suppliers and used without further purification or were
prepared according literature known procedures. Thin layer chromatography (TLC) analyses were
performed on TLC plates purchased from Merck (silica gel 60, fluorescence indicator F254, 0.25 mm layer
thickness). Products were purified by flash chromatography on silica gel 60 (230–400 mesh, Machery-
Nagel). NMR spectra were recorded with Bruker (AC 500) and JOEL (ECX 400, Eclipse 500) instruments.
1
13
Chemical shifts are reported relative to solvent residual peaks: H: ! = 7.26 ppm (CDCl
3
), C: ! = 77.0 ppm
1
13
(
CDCl ) and H: ! = 2.49 ppm (DMSO-d ), C: ! = 39.5 ppm (DMSO-d ). Integrals are in accordance with
3
6
6
13
assignments, and coupling constants are given in Hz. All C-NMR spectra are proton-decoupled. IR
spectra were measured with a Jasco FT/IR-4100 spectrometer. HRMS analyses were performed with a
Varian Ionspec QFT-7 (ESI-FT ICRMS) instrument. Melting points were measured with a Reichert
apparatus (Thermovar) and are uncorrected.
Experimental Procedures
Experimental Procedure A: To a solution of 1,2,4-trimethoxybenzene (1.0 equiv.) and aldehyde (0.7
equiv.) in MeCN (2.5 mL/mmol) at 0 °C was added F
stirred at room temperature until complete conversion of the arene. The reaction was quenched by addition
of sat. aqueous sodium bicarbonate solution (Na CO , aq.). The resulting mixture was extracted twice with
EtOAc. The combined organic phases were dried (Na SO ) and the solvent is removed in vacuo. The
residue was purified by column chromatography on silica gel.
3 3
CSO H (0.1 equiv), and the resulting mixture was
2
3
2
4
Experimental Procedure B: To a solution of 1-(4-methoxyphenyl)but-3-en-1-ol (1.0 equiv.) and
nucleophile (1.0 – 2.0 equiv.) in MeCN (2.5 mL/mmol) at 0 °C was added F CSO H (0.1 equiv), and the
resulting mixture was stirred at room temperature until complete conversion of the alcohol. The reaction
was quenched by addition of sat. aqueous sodium bicarbonate solution (Na CO , aq.). The resulting
mixture was extracted twice with EtOAc. The combined organic phases were dried (Na SO ) and the
solvent was removed in vacuo. The residue was purified by column chromatography on silica gel.
3
3
2
3
2
4

Characterization Data
Bis(2,4,5-trimethoxyphenyl)methane (5)
OMe
MeO
OMe
MeO
MeO
OMe
According to experimental procedure A: 1,2,4-trimethoxybenzene (336 mg, 2.00 mmol), paraformaldehyde
42 mg, 1.40 mmol), MeCN (5 mL), F CSO H (18 !L, 0.20 mmol), 1 h, rt; purification by column
(
3
3
chromatography (silica gel, ethyl acetate/hexane = 1:2) afforded 5 (399 mg, 99%) as colorless solid.
1
M. p. 97 – 98 °C. H NMR (500 MHz, CDCl
3
): ! = 3.75, 3.80 (2 s, 6 H each, OMe), 3.83 (s, 2 H, CH
2
), 3.87
), 56.1, 56.4,
6.5 (3 q, OMe), 97.7, 114.5 (2 d, Ar), 121.0, 142.8, 147.7, 151.5 (4 s, Ar) ppm. IR (film): " = 2995 – 2830
13
(
3 2
s, 6 H, OMe), 6.53, 6.66 (2 s, 2 H each, Ar) ppm. C NMR (126 MHz, CDCl ): ! = 28.7 (t, CH
5
-
1
+
(
C-H), 1610, 1515, 1465, 1440, 1395 cm . ESI-TOF: m/z calc. for [M+Na] : 371.1471, found 371.1457.
Anal. calc. for C19 (348.4): C 65.50, H 6.94; found: C 65.49, H 6.93.
Compound is literature known, see: [1].
24 6
H O
5
,5'-[(2-Bromophenyl)methylene]bis(1,2,4-trimethoxybenzene) (6a)
OMe
OMe
MeO
Br
MeO
MeO
OMe
According to experimental procedure A: 1,2,4-trimethoxybenzene (356 mg, 2.12 mmol), 2-bromo-
benzaldehyde (259 mg, 1.40 mmol), MeCN (5 mL), F CSO H (18 !L, 0.20 mmol), 24 h, rt; purification by
3
3
column chromatography (silica gel, ethyl acetate/hexane = 1:4 ! 1:2) afforded 6a (520 mg, 97%) as
colorless solid.
1
M. p. 162 – 164 °C. H NMR (500 MHz, CDCl
3
): ! = 3.61, 3.67, 3.88 (3 s, 6 H each, OMe), 6.27 (s, 1 H,
CH), 6.31, 6.54 (2 s, 2 H each, Ar), 6.87 (dd, J = 1.7, 7.7 Hz, 1 H, Ar), 7.04 (dt, J = 1.7, 7.6 Hz, 1 H, Ar),
1
3
7
.16 (dt, J = 1.4, 7.6 Hz, 1 H, Ar m, 1 H, Ph), 7.53 (dd, J = 1.4, 8.0 Hz, 1 H, Ar) ppm. C NMR (126 MHz,
CDCl ): ! = 43.0 (d, CH), 56.0, 56.6, 57.0 (3 q, OMe), 98.4, 114.3 (2 d, Ar), 123.0, 125.4 (2 s, Ar), 126.7,
27.5, 130.1, 132.9 (4 d, Ar), 142.6, 143.7, 148.2, 151.7 (4 s, Ar) ppm. IR (film): " = 3000 – 2845 (C-H),
3
1
1
5
-
1
+
610, 1510, 1465, 1440 cm . ESI-TOF: m/z calc. for [M+Na] : 525.0883; 527.0868, found 525.0900;
27.0884. Anal. calc. for C25 (503.4): C 59.65, H 5.41; found: C 59.74, H 5.41.
H
27BrO
6

5
,5'-[(4-Bromophenyl)methylene]bis(1,2,4-trimethoxybenzene) (6b)
OMe
OMe
MeO
MeO
MeO
OMe
Br
According to experimental procedure A: 1,2,4-trimethoxybenzene (336 mg, 2.00 mmol), 4-bromo-
benzaldehyde (259 mg, 1.40 mmol), MeCN (5 mL), F CSO H (18 !L, 0.20 mmol), 24 h, rt; purification by
3
3
column chromatography (silica gel, ethyl acetate/hexane = 1:4 ! 1:2) afforded 6b (486 mg, 96%) as
colorless solid.
1
M. p. 165 – 167 °C. H NMR (500 MHz, CDCl
3
): ! = 3.63, 3.66, 3.88 (3 s, 6 H each, OMe), 6.00 (s, 1 H,
CH), 6.39, 6.53 (2 s, 2 H each, Ar), 6.91, 7.34 (2 d, J = 8.4 Hz, 2 H each, Ar) ppm. Anal. calc. for
(503.4): C 59.65, H 5.41; found: C 59.72, H 5.48.
Compound is literature known, see: [2].
25 6
C H27BrO
5
,5'-[(4-Nitrophenyl)methylene]bis(1,2,4-trimethoxybenzene) (6c)
OMe
OMe
MeO
MeO
MeO
OMe
NO2
According to experimental procedure A: 1,2,4-trimethoxybenzene (336 mg, 2.00 mmol), 4-nitro-
benzaldehyde (211 mg, 1.40 mmol), MeCN (5 mL), F CSO H (18 !L, 0.20 mmol), 24 h, rt; purification by
3
3
column chromatography (silica gel, ethyl acetate/hexane = 1:4 ! 1:1) afforded 6c (456 mg, 97%) as bright
yellow solid.
1
M. p. 121 – 124 °C. H NMR (500 MHz, CDCl
3
): ! = 3.64, 3.66, 3.89 (3 s, 6 H each, OMe), 6.10 (s, 1 H,
CH), 6.38, 6.55 (2 s, 2 H each, Ar), 7.19, 8.08 (2 d, J = 8.7 Hz, 2 H each, Ar) ppm. Anal. calc. for
(514.4): C 63.96, H 5.80, N 2.98; found: C 63.95, H 6.12, N 2.97.
Compound is literature known, see: [2].
25 8
C H27NO
5
,5'-[(Perfluorophenyl)methylene]bis(1,2,4-trimethoxybenzene) (6d)
OMe
OMe
MeO
F
MeO
MeO
F
F
OMe
F
F
According to experimental procedure A: 1,2,4-trimethoxybenzene (400 mg, 2.38 mmol), 2,3,4,5,6-penta-
fluorobenzaldehyde (326 mg, 1.66 mmol), MeCN (6 mL), F CSO H (21 !L, 0.24 mmol), 2 h, rt; purification
3
3
by column chromatography (silica gel, ethyl acetate/hexane = 1:4 ! 3:2) afforded 6d (563 mg, 92%) as
colorless solid.

1
M. P. 127 – 129 °C. H NMR (500 MHz, CDCl
3
): ! = 3.69, 3.70, 3.88 (3 s, 6 H each, OMe), 6.24 (s, 1 H,
CH), 6.52, 6.56 (2 s, 2 H each, Ar) ppm. C NMR (126 MHz, CDCl ): ! = 33.7 (d, CH), 56.0, 56.5, 56.8 (3
q, OMe), 97.6, 114.0 (2 d, Ar), 119.8, 142.7, 148.9, 151.4 (4 s, Ar) ppm. F NMR (376 MHz, CDCl
63.1 (dt, J = 7.2, 21.2 Hz, 3-F), -157.7 (t, J = 21.2 Hz, 4-F), -140.7 (dd, J = 7.2, 22.0 Hz, 2-F) ppm. IR
13
3
19
3
) ! = -
1
-
1
+
(
film): " = 3015 – 2850 (C-H), 1735, 1610, 1520, 1500, 1465, 1440 cm . ESI-TOF: m/z calc. for [M+Na] :
5
23 5 6
37.1312, found 537.1303. Anal. calc. for C25H F O (514.4): C 58.37, H 4.51; found: C 59.06, H 4.57.
5
,5'-[(3,4-Dimethoxyphenyl)methylene]bis(1,2,4-trimethoxybenzene) (6e)
OMe
OMe
MeO
MeO
MeO
OMe
OMe
OMe
According to experimental procedure A: 1,2,4-trimethoxybenzene (354 mg, 2.10 mmol), 3,4-
dimethoxybenzaldehyde (244 mg, 1.47 mmol), MeCN (5 mL), F CSO H (18 !L, 0.20 mmol), 24 h, rt;
purification by column chromatography (silica gel, ethyl acetate/hexane = 1:2 ! 1:1) afforded 6e (320 mg,
3
3
6
3%) as colorless solid.
1
M. p. 112 – 115 °C. H NMR (500 MHz, CDCl
3
): ! = 3.62, 3.66 (2 s, 6 H each, OMe), 3.74, 3.82 (2 s, 3 H
each, OMe), 3.86 (s, 6 H, OMe), 6.00 (s, 1 H, CH), 6.41 (s, 2 H, Ar), 6.49 (dd, J = 1.4, 8.2 Hz, 1 H, Ar), 6.53
s, 2 H, Ar), 6.63 (d, J = 1.4 Hz, 1 H, Ar), 6.72 (d, J = 8.2 Hz, 1 H, Ar) ppm. Anal. calc. for C27 (484.5):
(
32 8
H O
C 66.93, H 6.66; found: C 66.92, H 6.66.
Compound is literature known, see: [2].
4
-[Bis(2,4,5-trimethoxyphenyl)methyl]-2-methoxyphenol (6f)
OMe
OMe
MeO
MeO
MeO
OMe
OH
OMe
According to experimental procedure A: 1,2,4-trimethoxybenzene (336 mg, 2.00 mmol), vanilin (214 mg,
.40 mmol), MeCN (5 mL), F CSO H (18 !L, 0.20 mmol), 24 h, rt; purification by column chromatography
1
3
3
(
silica gel, ethyl acetate/hexane = 1:3 ! 1:1) afforded 6f (294 mg, 62%) as colorless solid.
1
M. p. 188 – 190 °C. H NMR (500 MHz, CDCl
3
): ! = 3.64, 3.67 (2 s, 6 H each, OMe), 3.74 (s, 3 H, OMe),
3
.88 (s, 6 H, OMe), 5.49 (s, 1 H, OH), 5.99 (s, 1 H, CH), 6.43 (s, 2 H, Ar), 6.47 (ddd, J = 0.7, 2.0, 8.2 Hz, 1
13
H, Ar), 6.54 (s, 2 H, Ar), 6.61 (d, J = 2.0 Hz, 1 H, Ar), 6.78 (d, J = 8.2 Hz, 1 H, Ar) ppm. C NMR (126 MHz,
CDCl ): ! = 42.1 (d, CH), 55.8, 56.1, 56.7, 57.0 (4 q, OMe), 98.4, 111.9, 113.7, 114.4, 121.5 (5 d, Ar),
24.8, 136.1, 142.7, 143.6, 146.2, 147.9, 151.5 (7 s, Ar) ppm. IR (film): " = 3440 (OH), 3000 – 2835 (C-H),
3
1
1
-
1
+
610, 1510, 1465, 1440 cm . ESI-TOF: m/z calc. for [M+Na] : 493.1838, found 493.1847. Anal. calc. for
(470.2): C 66.37, H 6.43; found: C 66.40, H 6.43.
Compound is literature known, see: [3].
26 30 8
C H O

{
4-[Bis(2,4,5-trimethoxyphenyl)methyl]phenyl}boronic acid (6g)
OMe
OMe
MeO
MeO
MeO
OH
OMe
B
OH
According to experimental procedure A: 1,2,4-trimethoxybenzene (672 mg, 4.00 mmol), (4-formyl-
phenyl)boronic acid (150 mg, 1.00 mmol), MeCN (5 mL), F CSO H (9 !L, 0.10 mmol), 24 h, rt; purification
3
3
by precipitation (diethylether/hexane) afforded 6g (407 mg, 92%) as colorless solid.
1
M. p. 100 – 120 °C. H NMR (500 MHz, CDCl
3
): ! = 3.63, 3.67, 3.89 (3 s, 6 H each, OMe), 6.13 (s, 1 H,
13
CH), 6.44, 6.55 (2 s, 2 H each, Ar), 7.18, 8.08 (2 d, J = 7.9 Hz, 2 H each, Ph) ppm. C NMR (126 MHz,
CDCl ): ! = 43.0 (d, CH), 56.0, 56.6, 56.9 (3 q, OMe), 98.2, 114.4 (2 d, Ar), 123.9 (s, Ar), 128.7, 135.3 (2 d,
Ar), 142.7, 148.1, 149.4, 151.6 (4 s, Ar) ppm. IR (film): " = 3480 (OH), 3000 – 2830 (C-H), 1605, 1510,
3
"
1
1
8
460 cm . Anal. calc. for C25H29BO (468.3): C 64.12, H 6.24; found: C 64.43, H 6.08.
3
-[Bis(2,4,5-trimethoxyphenyl)methyl]pyridine (6h)
OMe
OMe
MeO
2
MeO
MeO
3
N
4
6
OMe
5
According to experimental procedure A: 1,2,4-trimethoxybenzene (164 mg, 0.98 mmol), nicotinaldehyde
75 mg, 0.70 mmol), MeCN (2.5 mL), F CSO H (97 !L, 1.10 mmol), 24 h, rt; purification by column
(
3
3
chromatography (silica gel, ethyl acetate/hexane = 1:2 ! 1:1) afforded 6h (207 mg, 99%) as colorless
solid.
1
M. p. 114 – 116 °C. H NMR (500 MHz, CDCl
3
): ! = 3.63, 3.66, 3.88 (3 s, 6 H each, OMe), 6.04 (s, 1 H,
CH), 6.40, 6.54 (2 s, 2 H each, Ar), 7.17 (dd, J = 4.8, 7.9 Hz, 5-H), 7.33 (dt, J = 2.0, 7.9 Hz, 1 H, 4-H), 8.32
1
3
(
d, J = 2.3 Hz, 1 H, 2-H), 8.41 (dd, J = 1.7, 4.8 Hz, 1 H, 6-H) ppm. C NMR (126 MHz, CDCl
CH), 56.0, 56.6, 56.7 (3 q, OMe), 98.1, 114.4 (2 d, Ar), 122.7 (s, Ar), 122.9 (d, C-5), 136.3 (d, C-4), 139.8,
42.7 (2 s, Ar), 147.0 (d, C-6), 148.4 (s, Ar), 150.5 (d, C-2), 151.4 (s, Ar) ppm. IR (film): " = 3000 – 2835
3
): ! = 40.6 (d,
1
"
1
+
(
C-H), 1510, 1465, 1440 cm . ESI-TOF: m/z calc. for [M+Na] : 426.1911, found 426.1919. Anal. calc. for
24 6
C H27NO
(425.5): C 67.75, H 6.40, N 3.29; found: C 67.75, H 6.47, N 3.30.
5
,5'-(Pentane-1,1-diyl)bis(1,2,4-trimethoxybenzene) (7a)
OMe
OMe
MeO
MeO
MeO
2
4
1
3
5
Me
OMe

According to experimental procedure A: 1,2,4-trimethoxybenzene (168 mg, 1.00 mmol), pentanal (60 mg,
.70 mmol), MeCN (5 mL), F CSO H (9 !L, 0.10 mmol), 6 h, rt; purification by column chromatography
silica gel, ethyl acetate/hexane = 1:4 ! 1:2) afforded 7a (181 mg, 89%) as colorless oil.
0
3
3
(
1
H NMR (500 MHz, CDCl
.89 (m , 2 H, 2-H), 3.74, 3.79, 3.85 (3 s, 6 H each, OMe), 4.57 (t, J = 7.8 Hz, 1 H, 1-H), 6.50, 6.79 (2 s, 2
H each, Ar) ppm. C NMR (126 MHz, CDCl
6.5 (d, C-1), 56.0, 56.7, 56.9 (3 q, OMe), 98.4, 112.9 (2 d, Ar), 125.6, 142.8, 147.5, 151.6 (4 s, Ar) ppm.
3 c
): ! = 0.86 (t, J = 7.4 Hz, 3 H, 5-H), 1.23 – 1.27 (m, 2 H, 4-H), 1.32 (m , 2 H, 3-H),
1
c
13
3
): ! = 14.0 (q, C-5), 22.6 (t, C-4), 30.1 (t, C-3), 34.2 (t, C-2),
3
"
1
+
IR (film): " = 2995 – 2830 (C-H), 1610, 1510, 1465, 1395 cm . ESI-TOF: m/z calc. for [M+Na] : 427.2097,
found 427.2065. Anal. calc. for C23 (404.5): C 68.29, H 7.97; found: C 68.16, H 7.90.
32 6
H O
5
,5'-(Dodecane-1,1-diyl)bis(1,2,4-trimethoxybenzene) (7b)
OMe
OMe
MeO
2
1
12
MeO
MeO
3
Me
OMe
According to experimental procedure A: 1,2,4-trimethoxybenzene (339 mg, 2.02 mmol), dodecanal (258
mg, 1.40 mmol), MeCN (5 mL), F CSO H (18 !L, 0.20 mmol), 24 h, rt; purification by column
3
3
chromatography (silica gel, ethyl acetate/hexane = 1:4 ! 1:1) afforded 7b (398 mg, 79%) as slightly
brownish oil.
1
H NMR (500 MHz, DMSO-d
6
): ! = 0.84 (t, J = 7.1 Hz, 3 H, 12-H), 1.12 – 1.26 (m, 18 H, 3-H to 11-H), 1.78
–
1.87 (m, 2 H, 2-H), 3.64, 3.70, 3.74 (3 s, 6 H each, OMe), 4.51 (t, J = 7.9 Hz, 1 H, 1-H), 6.60, 6.78 (2 s, 2
1
3
H each, Ar) ppm. C NMR (126 MHz, DMSO-d
6
): ! = 13.9 (q, C-12), 22.1, 27.5, 28.7, 28.8, 28.9, 28.97,
9.00, 31.3, 34.0, 35.3 (10 t, C-2 to C-11), 55.7, 56.4, 56.6 (3 q, OMe), 98.9, 113.6 (2 d, Ar), 124.5, 142.4,
47.6, 151.3 (4 s, Ar) ppm (the signal of C-1 overlaps with solvent residue peak). IR (film): " = 2990 – 2850
2
1
"
1
+
(
C-H), 1610, 1510, 1465, 1440 cm . ESI-TOF: m/z calc. for [M+Na] : 525.3192, found 525.3198. Anal.
calc. for C30 (502.7): C 71.68, H 9.22; found: C 71.68, H 9.20.
46 6
H O
5
,5'-(Cyclohexylmethylene)bis(1,2,4-trimethoxybenzene) (7c)
OMe
OMe
MeO
MeO
MeO
OMe
According to experimental procedure A: 1,2,4-trimethoxybenzene (336 mg, 2.00 mmol), cyclohexyl-
aldehyde (244 mg, 1.47 mmol), MeCN (5 mL), F CSO H (18 !L, 0.20 mmol), 24 h, rt; purification by
3
3
column chromatography (silica gel, ethyl acetate/hexane = 1:4 ! 1:3) afforded 7c (320 mg, 83%) as
brownish highly viscous oil.
1
3
H NMR (500 MHz, CDCl ): ! = 0.87 – 0.93 (m, 2 H, Cy), 1.10 – 1.21 (m, 3 H, Cy), 1.54 – 1.70 (m, 5 H,
Cy), 2.04 – 2.11 (m, 1 H, Cy), 3.76, 3.818, 3.824 (3 s, 3 H each, OMe), 4.28 (d, J = 11.3 Hz, 1 H, CH),

6
7
.46, 6.93 (2 s, 2 H each, Ar) ppm. Anal. calc. for C25
34 6
H O (430.5): C 69.74, H 7.96 found: C 69.75, H
.79.
Compound is literature known, see: [2].
5
,5'-(2,2-Dimethylpropane-1,1-diyl)bis(1,2,4-trimethoxybenzene) (7d)
OMe
OMe
MeO
MeO
MeO
1
t-Bu
OMe
According to experimental procedure A: 1,2,4-trimethoxybenzene (321 mg, 1.91 mmol), pivaldehyde (115
mg, 1.34 mmol), MeCN (5 mL), F CSO H (17 !L, 0.19 mmol), 24 h, rt; purification by column
3
3
chromatography (silica gel, ethyl acetate/hexane = 1:3) afforded 7d (233 mg, 58%) as colorless oil.
1
3
H NMR (500 MHz, CDCl ): ! = 1.02 (s, 9 H, t-Bu), 3.76, 3.83, 3.84 (3 s, 6 H each, OMe), 5.00 (s, 1 H, 1-
1
3
H), 6.50, 7.15 (2 s, 2 H each, Ar) ppm. C NMR (126 MHz, CDCl
3
): ! = 29.2, 35.7 (q, s, t-Bu), 41.4 (d, C-
1
2
4
), 55.9, 56.7, 57.4 (3 q, OMe), 98.8, 114.6 (2 d, Ar), 124.5, 142.5, 147.5, 152.4 (4 s, Ar) ppm. IR (film): " =
"
1
+
950 – 2835 (C"H), 1610, 1590, 1510, 1465, 1440 cm . ESI-TOF: m/z calc. for [M+Na] : 427.2097, found
27.2091. Anal. calc. for C23 (404.5): C 68.29, H 7.97; found: C 68.31, H 7.98.
32 6
H O
5
,5'-(2-Bromoethane-1,1-diyl)bis(1,2,4-trimethoxybenzene) (7e)
OMe
OMe
MeO
MeO
MeO
2
Br
1
OMe
According to experimental procedure A: 1,2,4-trimethoxybenzene (336 mg, 2.00 mmol), 2-bromo-1,1-
diethoxyethane (275 mg, 1.40 mmol), MeCN (5 mL), F CSO H (18 !L, 0.20 mmol), 2 h, rt; purification by
3
3
column chromatography (silica gel, ethyl acetate/hexane = 1:4 ! 1:2) afforded 7e (334 mg, 76%) as
colorless oil.
1
H NMR (500 MHz, CDCl
t, J = 8.0 Hz, 1 H, 1-H), 6.51, 6.73 (2 s, 2 H each, Ar) ppm. C NMR (126 MHz, CDCl
1.1 (d, C-1), 55.8, 56.4, 56.6 (3 q, OMe), 97.8, 113.1 (2 d, Ar), 121.0, 142.5, 148.3, 151.6 (4 s, Ar) ppm.
3
): ! = 3.76, 3.77, 3.85 (3 s, 6 H each, OMe), 3.90 (d, J = 8.0 Hz, 2 H, 2-H), 4.92
13
(
3
): ! = 34.4 (t, C-2),
4
"
1
IR (film): " = 2995 – 2830 (C"H), 1615, 1610, 1510, 1465, 1440 cm . ESI-TOF: m/z calc. for [M+Na–
+
HBr] : 383.1471, found 383.1489. Anal. calc. for C20
H
25BrO
6
(441.3): C 54.43, H 5.71; found: C 54.35, H
5
.48.
Diethyl [2,2-bis(2,4,5-trimethoxyphenyl)ethyl]phosphonate (7f)

OMe
OMe
MeO
O
P
MeO
MeO
2
1
OEt
OEt
OMe
According to experimental procedure A: 1,2,4-trimethoxybenzene (336 mg, 2.00 mmol), diethyl(2,2-
diethoxyethyl)phosphonate (356 mg, 1.40 mmol), MeCN (5 mL), F CSO H (18 !L, 0.20 mmol), 24 h, rt;
3
3
purification by column chromatography (silica gel, ethyl acetate/hexane
=
1:3
!
dichloro-
methane/diethylether 1:1) afforded 7f (298 mg, 60%) as brownish oil.
1
1
H NMR (500 MHz, CDCl
3
): ! = 1.12 (t, J = 7.1 Hz, 6 H, P(OEt), 2.61 (dd, JPH = 18.0 Hz, J = 7.6, 2 H, 1-H),
2
3
.74, 3.78, 3.82 (3 s, 6 H each, OMe), 4.83 (dt, JPH = 15.3, J = 7.6, 1 H, 2-H), 6.45, 6.87 (2 s, 2 H each,
1
3
3
1
Ar) ppm. C NMR (126 MHz, CDCl
3
): ! = 16.2 (dq, JPC = 6.3 Hz, P(OEt)
2
), 29.6 (dt, JPC = 138.0 Hz, C-1),
2
2
3
4.4 (dd, JPC = 2.5 Hz, C-2), 56.0, 56.3, 56.6 (3 q, OMe), 61.1 (dt, JPC = 6.4 Hz, P(OEt)
2
), 97.8, 113.8 (2
3
31
d, Ar), 123.2 (d, JPC = 10.3 Hz, Ar), 142.4, 148.0, 151.3 (3 s, Ar) ppm. P NMR (162 MHz, CDCl
3
): ! =
"
1
+
3
5
1.3 ppm. IR (film): " = 2985 – 2835 (C"H), 1610, 1510, 1465, 1440 cm . ESI-TOF: m/z calc. for [M+Na] :
35 9
21.1916, found 521.1917. Anal. calc. for C24H O P (498.5): C 57.82, H 7.08; found: C 57.73, H 7.13.
3
,3-Bis(2,4,5-trimethoxyphenyl)propanenitrile (7g)
OMe
OMe
MeO
MeO
MeO
2
CN
3
1
OMe
According to experimental procedure A: 1,2,4-trimethoxybenzene (345 mg, 2.05 mmol), 3,3-dimethoxy-
propanenitrile (165 mg, 1.43 mmol), MeCN (5 mL), F CSO H (18 !L, 0.20 mmol), 24 h, rt; purification by
3
3
column chromatography (silica gel, ethyl acetate/hexane = 1:2 ! 1:1) afforded 7g (233 mg, 55%) as
colorless highly viscous oil.
1
H NMR (500 MHz, CDCl
t, J = 7.7 Hz, 1 H, 3-H), 6.52, 6.73 (2 s, 2 H each, Ar) ppm. C NMR (126 MHz, CDCl
5.8 (d, C-3), 56.0, 56.3, 56.7 (3 q, OMe), 97.7, 113.1 (2 d, Ar), 119.3 (s, C-1), 120.6, 142.8, 148.7, 151.3
3
): ! = 3.05 (d, J = 7.7 Hz, 2 H, 2-H), 3.76, 3.79, 3.87 (3 s, 6 H each, OMe), 4.87
13
(
3
): ! = 21.7 (t, C-2),
3
"
1
(
4 s, Ar) ppm. IR (film): " = 3000 – 2835 (C"H), 2245, 1610, 1510, 1465, 1440 cm . ESI-TOF: m/z calc. for
+
[
M+Na] : 410.1580, found 410.1616. Anal. calc. for C21
H
25NO
6
(387.4): C 65.10, H 6.50; found: C 65.15, H
6
.54.
4
,4-Bis(2,4,5-trimethoxyphenyl)butan-2-one (7h)
OMe
OMe
MeO
O
2
1
MeO
MeO
3
4
OMe

According to experimental procedure A: 1,2,4-trimethoxybenzene (336 mg, 2.00 mmol), 4,4-dimethoxy-
butan-2-one (185 mg, 1.40 mmol), MeCN (5 mL), F CSO H (18 !L, 0.20 mmol), 24 h, rt; purification by
3
3
column chromatography (silica gel, ethyl acetate/hexane = 2:3) afforded 7h (339 mg, 84%) as yellow solid.
1
M. p. 98 – 100 °C. H-NMR (500 MHz, CDCl
3
): ! = 2.08 (s, 3 H, 1-H), 3.07 (d, J = 7.9 Hz, 2 H, 3-H), 3.76 (s,
1
3
1
2 H, OMe), 3.84 (s, 6 H, OMe), 5.06 (t, J = 7.9 Hz, 1 H, 4-H), 6.49, 6.71 (2 s, 2 H each, Ar) ppm. C NMR
126 MHz, CDCl ): ! = 29.6 (q, C-1), 34.4 (d, C-4), 48.4 (t, C-3), 56.1, 56.5, 56.7 (3 q, OMe), 98.1, 113.2 (2
d, Ar), 123.2, 142.7, 148.0, 151.3 (4 s, Ar), 208.1 (s, C-2) ppm. IR (film): " = 2995 – 2835 (C"H), 1710
(
3
"
1
+
(
C=O), 1610, 1510, 1465, 1440 cm . ESI-TOF: m/z calc. for [M+Na] : 427.1733, found 427.1745. Anal.
calc. for C22 (404.5): C 65.33, H 6.98; found: C 65.45, H 6.67.
28 7
H O
Methyl 4,4-bis(2,4,5-trimethoxyphenyl)butanoate (7i)
OMe
OMe
MeO
1
MeO
MeO
3
4
2 CO Me
2
OMe
According to experimental procedure A: 1,2,4-trimethoxybenzene (336 mg, 2.00 mmol), methyl 2-
trimethylsiloxy)cyclopropanecarboxylate (263 mg, 1.40 mmol), MeCN (5 mL), F CSO H (18 !L, 0.20
(
3
3
mmol), 30 min, 0 °C; purification by column chromatography (silica gel, ethyl acetate/hexane = 1:3 ! 1:1)
afforded 7i (421 mg, 97%) as colorless oil.
1
3 2
H NMR (500 MHz, CDCl ): ! = 2.21 – 2.30 (m, 4 H, 2-H, 3-H), 3.61 (3 H, CO Me), 3.72, 3.78, 3.84 (3 s, 6
13
H each, OMe), 4.55 (t, J = 7.3 Hz, 1 H, 4-H), 6.48, 6.78 (2 s, 2 H each, Ar) ppm. C NMR (126 MHz,
CDCl ): ! = 29.4 (t, C-2), 32.6 (t, C-3), 36.2 (d, C-4), 51.3, 56.0, 56.66, 56.68 (4 q, OMe), 98.2, 112.7 (2 d,
Ar), 124.2, 142.8, 147.8, 151.6 (4 s, Ar), 174.2 (s, C-1) ppm. IR (film): " = 2995 – 2830 (C-H), 1735 (C=O),
3
-
1
+
1
610, 1510, 1465, 1455, 1440, 1395 cm . ESI-TOF: m/z calc. for [M+Na] : 457.1838, found 457.1838.
Anal. calc. for C23 (434.5): C 63.58, H 6.96; found: C 63.60, H 7.00.
30 8
H O
(
S)-1,1-Bis(2,4,5-trimethoxyphenyl)propan-2-ol (Tatarinoid C)
OMe
MeO
OMe
OH
1
2
MeO
MeO
3
Me
OMe
According to experimental procedure A: 1,2,4-trimethoxybenzene (673 mg, 4.00 mmol), (S)-2-(tert-
butyldimethylsiloxy)propanal (452 mg, 2.40 mmol), MeCN (20 mL), F CSO H (18 !L, 0.20 mmol), 6 h, rt;
3
3
purification by column chromatography (silica gel, ethyl acetate/hexane = 1:1) afforded (-)-tatarinoid C (343
mg, 44%) as colorless oil.
2
D
2
1
[!]
3 3
= -6.2 (c = 2.55, CHCl ). H NMR (500 MHz, CDCl ): ! = 1.17 (d, J = 5.7 Hz, 3 H, 3-H), 1.95 (bs, 1 H,
OH), 3.758, 3.761, 3.77, 3.81, 3.83, 3.84 (6 s, 3 H each, OMe), 4.51 – 4.58 (m, 2 H, 1-H, 2-H), 6.48, 6.51,
1
3
6
3
.91, 7.06 (4 s, 1 H each, Ar) ppm. C NMR (126 MHz, CDCl ): ! = 21.5 (q, C-3), 45.7 (d, C-1), 55.90,

5
1
1
5.91, 56.53, 56.54, 56.6, 56.7 (6 q, OMe), 69.5 (d, C-2), 98.1, 98.3, 113.6, 113.7 (4 d, Ar), 121.3, 122.9,
42.7, 142.9, 147.8, 148.0, 151.3, 152.0 (8 s, Ar) ppm. IR (film): " = 3490 (OH), 2950 – 2830 (C-H), 1610,
-
1
+
510, 1465, 1440, 1395 cm . ESI-TOF: m/z calc. for [M+Na] : 415.1733, found 415.1754. Anal. calc. for
21 28 7
C H O
(392.4): C 64.27, H 7.19; found: C 64.23, H 7.18.
(
S)-(S)-1,1-Bis(2,4,5-trimethoxyphenyl)propan-2-yl-3,3,3-trifluoro-2-methoxy-2-phenylpropanoate
OMe
MeO
OMe Ph
1
´´
OMe
MeO
MeO
O 4´´
5
´´
2
´´
CF3
3
´´Me
O
OMe
To a solution of (–)-tatarinoid C (60 mg, 0.15 mmol) in dichloromethane (2.0 mL) was added i-Pr
L, 0.31 mmol), (R)-(-)-!-methoxy-!-(trifluoromethyl)phenylacetylchloride (62 mg, 0.26 mmol) and DMAP
4 mg, 0.03 mmol), and the resulting mixture was stirred for 6 h until complete conversion of (-)-tatarinoid.
The reaction was quenched by addition of water; the resulting mixture was extracted twice with
2
NEt (51
!
(
dichloromethane. The combined organic layers were dried (Na
2
SO
4
) and the solvent was removed in
1
vavuo. The diastereomeric ratio (d. r.) was determined to be >98:2 by analysis of crude product by H- and
19
F-NMR spectroscopy. Further purification by column chromatography (silica gel, ethyl acetate/hexane =
1
:4 ! 1:1) afforded Mosher ester derivative (70 mg, 75%) as colorless solid.
2
D
2
1
M. p. 34 – 36 °C. [!]
3 3
= -70.9 (c = 0.22, CHCl ). H NMR (500 MHz, CDCl ): ! = 1.23 (d, J = 6.2 Hz, 3 H,
3
8
7
´´-H), 3.23 (s, 3 H, C(5´´)-OMe), 3.687, 3.690, 3.73, 3.846, 3.850, 3.852 (6 s, je 3 H, OMe), 4.87 (d, J =
.9 Hz, 1 H, 1´´-H), 6.18 (m , 1 H, 2´´-H), 6.47, 6.50, 6.79 (3 s, je 1 H, Ar), 7.10 – 7.12 (m, 2 H, Ph), 7.16 –
.21 (m, 3 H, Ar, Ph), 7.28 – 7.31 (m, 1 H, Ph) ppm. C NMR (126 MHz, CDCl
c
13
3
): ! = 18.6 (q, C-3´´), 42.9
2
(
d, C-1´´), 54.9 (d, C(5´´)-OMe), 55.9*, 56.30, 56.32, 56.4, 56.6 (6 q, OMe), 74.9 (d, C-2´´), 84.4 (q, JCF
=
),
1
2
1
4
2
6
7.7 Hz, C-5´´), 97.7, 98.1, 113.1, 114.1 (4 d, Ar), 120.6, 120.8 (2 s, Ar), 123.3 (q, JCF = 288.5 Hz, CF
3
27.1, 128.1, 129.3 (3 d, Ph), 132.3 (s, Ph), 142.7, 142.8, 148.0, 148.2, 151.3, 151.7 (6 s, Ar), 166.2 (s, C-
1
9
´´) ppm; * signal with higher intensitiy. F NMR (470 MHz, CDCl
3
): ! = -71.0 (CF
3
) ppm. IR (film): " =
-
1
+
995 – 2830 (C-H), 1740 (C=O), 1610, 1510, 1465, 1455, 1440 cm . ESI-TOF: m/z calc. for [M+Na] :
35 3 9
31.2131, found 631.2095. Anal. calc. for C31H F O (608.5): C 61.18, H 5.80; found: C 61.38, H 5.95.
4
,4'-[(4-Bromophenyl)methylene]bis(1,2-dimethoxybenzene) (11)
OMe
OMe
MeO
Br
OMe
According to experimental procedure A: 1,2,-dimethoxybenzene (276 mg, 2.00 mmol), 4-bromo-
benzaldehyde (250 mg, 1.35 mmol), MeCN (2.5 mL), F CSO H (18 !L, 0.20 mmol), 24 h, rt; purification by
3
3
column chromatography (silica gel, ethyl acetate/hexane = 1:6 ! 1:2) afforded 11 (147 mg, 34%) as
colorless solid.

1
M. p. 149 – 152 °C. H NMR (500 MHz, CDCl
3
): ! = 3.76, 3.86 (2 s, 6 H each, OMe), 5.39 (s, 1 H, CH),
.56 (ddd, J = 0.7, 2.0, 8.2 Hz, 2 H, Ar), 6.63 (d, J = 2.0 Hz, 2 H, Ar), 6.78 (d, J = 8.2 Hz, 2 H, Ar), 6.98 (d, J
7.8 Hz, 2 H, Ar), 7.40 (d, J = 8.4 Hz, 2 H, Ar) ppm. Anal. calc. for C23 (443.3): C 62.31, H 5.23;
6
=
H
23BrO
4
found: C 62.31, H 5.44.
Compound is literature known, see: [4].
1
,2,4-Trimethoxy-5-[1-(4-methoxyphenyl)but-3-en-1-yl]benzene (14a)
OMe
MeO
OMe
1
3
2
4
MeO
According to experimental procedure B: 1-(4-methoxyphenyl)but-3-en-1-ol (201 mg, 1.13 mmol), 1,2,4-
trimethoxybenzene (172 mg, 1.02 mmol), MeCN (2.5 mL), F CSO H (9 !L, 0.10 mmol), 45 min, 0 °C;
3
3
purification by column chromatography (silica gel, ethyl acetate/hexane = 1:4) afforded 14a (338 mg, 99%)
as colorless oil.
1
H NMR (500 MHz, CDCl
.0 Hz, 1 H, 1-H), 4.93, 5.02 (2 m
6.82 (m, 2 H, Ar), 7.15 – 7.19 (m, 2 H, Ar) ppm. C NMR (126 MHz, CDCl
3
): ! = 2.73 (m
c
, 2 H, 2-H), 3.75, 3.77, 3.80, 3.86 (4 s, 3 H each, OMe), 4.39 (t, J =
, 1 H, 3-H), 6.50, 6.75 (2 s, 1 H each, Ar), 6.74
): ! = 39.4 (t, C-2), 42.1 (d, C-
8
–
1
1
1
c
, 1 H each, 4-H), 5.73 (m
c
1
3
3
), 55.1, 56.1, 56.6, 56.8 (4 q, OMe), 98.1, 112.4, 113.5 (3 d, Ar), 115.8 (t, C-4), 125.0 (s, Ar), 128.8 (d, Ar),
36.8 (s, Ar), 137.3 (d, C-3), 143.0, 147.8, 151.2, 157.6 (4 s, Ar) ppm. IR (film): " = 3005 – 2835 (C-H),
-
1
+
610, 1510, 1465, 1440 cm . ESI-TOF: m/z calc. for [M+Na] : 351.1567, found 351.1585. Anal. calc. for
20 24 4
C H O
(328.4): C 59.65, H 5.41; found: C 59.72, H 5.48.
3
-[1-(4-Methoxyphenyl)but-3-en-1-yl]-1H-indole (14b)
7
´
6
´
NH
2
5
´
´
4´
3
´
1
3
2
4
MeO
According to experimental procedure B: 1-(4-methoxyphenyl)but-3-en-1-ol (364 mg, 2.04 mmol), indole
242 mg, 2.07 mmol), MeCN (5 mL), F CSO H (18 !L, 0.10 mmol), 16 h, rt; purification by column
(
3
3
chromatography (silica gel, ethyl acetate/hexane = 1:7) afforded 14b (343 mg, 60%) as colorless highly
visous oil which slowly decomposes.
1
H NMR (500 MHz, CDCl
, 1 H each, 4-H), 5.85 (m
.03 – 7.06 (m, 2 H, Indole), 7.17 (m , 1 H, Indole), 7.33 (m
H, NH) ppm. C NMR (126 MHz, CDCl ): ! = 40.6 (t, C-2), 42.1 (d, C-1), 55.1 (q, OMe), 111.0 (d, Indole),
13.6 (d, Ar), 115.9 (t, C-4), 119.2, 119.5 (2 d, Indole), 120.0 (s, Indole), 121.2, 121.9 (2 d, Indole), 126.9
s, Ar), 128.8 (d, Ar), 136.5, 136.9 (2 s, Indole), 137.4 (d, C-3), 157.8 (s, Ar) ppm. IR (film): " = 3420 (N-H),
3
): ! = 2.78, 2.96 (2 m
c
, 1 H each, 2-H), 3.79 (s, 3 H, OMe), 4.26 (t, J = 7.4 Hz, 1
, 1 H, 3-H), 6.84, 7.23 (2 d, J = 8.7 Hz, 2 H each, Ar),
, 1 H, Indole), 7.45 (m , 1 H, Indole), 7.97 (bs, 1
H, 1-H), 4.99, 5.09 (2 m
c
c
7
c
c
c
13
3
1
(

-
1
+
3
3
000 – 2835 (C-H), 1610, 1510, 1455, 1440 cm . ESI-TOF (C19
H19NO (277.4): m/z calc. for [M+Na] :
00.1364, found 300.1382.
3
-[1-(4-Methoxyphenyl)but-3-en-1-yl]pentane-2,4-dione (14c)
O
O
1´
1
3
2
4
MeO
According to experimental procedure B: 1-(4-methoxyphenyl)but-3-en-1-ol (358 mg, 2.01 mmol), pentan-
,4-dione (401 mg, 4.01 mmol), MeCN (5 mL), F CSO H (18 !L, 0.10 mmol), 16 h, rt; purification by
2
3
3
column chromatography (silica gel, ethyl acetate/hexane = 1:6 ! 1:4) afforded 14c (387 mg, 74%) as
colorless oil.
1
H NMR (500 MHz, CDCl
3
): ! = 1.80, 2.24 (2 s, 3 H each, Me), 2.20 – 2.27 (m, 2 H, 2-H), 3.53 (m
, 1 H, 3-H), 6.80,
3
.04 (2 d, J = 8.7 Hz, 2 H each, Ar) ppm. C NMR (126 MHz, CDCl ): ! = 29.2, 30.1 (2 q, Me), 39.4 (t, C-
c
, 1 H, 1-
H), 3.75 (s, 3 H, OMe), 4.09 (d, J = 11.5 Hz, 1 H, 1´-H), 4.86 – 4.92 (m, 2 H, 4-H), 5.49 (m
c
13
7
2
1
1
), 44.6 (d, C-1), 55.1 (q, OMe), 75.4 (d, C-3), 114.0 (d, Ar), 117.1 (t, C-4), 129.1 (d, Ar), 132.2 (s, Ar),
35.0 (d, C-3), 158.4 (s, Ar), 203.2, 203.2 (2 s, C=O) ppm. IR (film): " = 3075 – 2840 (C-H), 1700 (C=O),
-
1
+
610, 1515, 1465, 1440 cm . ESI-TOF: m/z calc. for [M+Na] : 283.1310, found 283.1329. Anal. calc. for
16 20 3
C H O
(260.3): C 73.82, H 7.74; found: C 73.07, H 7.68.
1
-(Hepta-1,6-dien-4-yl)-4-methoxybenzene (14d)
1
3
2
4
MeO
According to experimental procedure B: 1-(4-methoxyphenyl)but-3-en-1-ol (80 mg, 0.45 mmol),
allyltrimethylsilane (103 mg, 0.90 mmol), MeCN (1.3 mL), F CSO H (2 !L, 0.02 mmol), 2 h, rt; purification
3
3
by column chromatography (silica gel, ethyl acetate/hexane = 1:20) afforded 14d (61 mg, 67%) as
colorless oil.
1
3 c c
H NMR (400 MHz, CDCl ): ! = 2.37 (m , 4 H, 2-H), 2.70 (m , 1 H, 1-H), 3.80 (s, 3 H, OMe), 4.94 – 5.02 (m,
4
H, 4-H), 5.69 (m , 2 H, 3-H), 6.86, 7.10 (2 d, J = 8.3 Hz, 2 H each, Ar) ppm.
c
Compound is literature known, see: [5].
N-[1-(4-Methoxyphenyl)but-3-en-1-yl]-4-methylbenzenesulfonamide (14e)
SO Tol
2
HN
1
3
2
4
MeO
According to experimental procedure B: 1-(4-methoxyphenyl)but-3-en-1-ol (81 mg, 0.45 mmol), p-
toluolsulfonamide (154 mg, 0.90 mmol), MeCN (1.3 mL), F CSO H (2 !L, 0.02 mmol), 24 h, rt; purification
3
3
by column chromatography (silica gel, ethyl acetate/hexane = 1:6 ! 1:4) afforded 14e (92 mg, 62%) as
colorless oil.

1
H NMR (500 MHz, CDCl
H, 1-H), 4.87 (bd, J = 6.1 Hz, 1 H, NH), 5.01 – 5.08 (m, 2 H, 4-H), 5.50 (m
.7 Hz, 1 H, each, Ar), 7.15, 7.54 (2 d, J = 8.3 Hz, 1 H, each, Ar) ppm.
Compound is literature known, see: [6].
3
): ! = 2.38 (s, 3 H, Me), 2.39 – 2.50 (m, 2 H, 2-H), 3.75 (s, 3 H, OMe), 4.31 (m
c
, 1
c
, 1 H, 3-H), 6.70, 6.98 (2 d, J =
8

[
[
1] Govindachari, T. R.; Nagarajan, K.; Parthasarathy, P. C. J. Chem. Soc. 1958, 899–916.
2] Jaratjaroonphong, J.; Sathalalai, S.; Techasauvapak, P.; Reutrakul, V. Tetrahedron Lett. 2009, 50,
6
012-6015.
[
[
3] Szeki, T. Ber. dtsch. Chem. Ges. 1911, 44, 1476-1481.
4] Mohammadpoor-Baltork, I.; Moghadam, M.; Tangestaninejad, S.; Mirkhani, V.; Mohammadiannejad-
Abbasabadi, K.; Khavasi, H. R. Eur. J. Org. Chem. 2011, 1357-1366.
5] Vennall, G. P.; Aggarwal, V. K. Synthesis 1998, 12, 1822-1826.
6] Thiruphati, P.; Kim, S. S. Tetrahedron 2010, 66, 8623-8628.
[
[

1H NMR: 5
OMe
OMe
OMe
MeO
MeO
MeO

13C NMR: 5
OMe
OMe
OMe
MeO
MeO
MeO

1H NMR: 6a
OMe
OMe
OMe
Br
MeO
MeO
MeO

13C NMR: 6a
OMe
OMe
OMe
Br
MeO
MeO
MeO

1H NMR: 6b
OMe
OMe
OMe
MeO
MeO
MeO
Br

1H NMR: 6c
OMe
OMe
OMe
MeO
MeO
MeO
NO2

OMe
1H NMR: 6d
OMe
F
MeO
MeO
F
F
MeO
OMe
F
F

OMe
13C NMR: 6d
OMe
F
MeO
MeO
F
F
MeO
OMe
F
F

OMe
19F NMR: 6d
OMe
F
MeO
MeO
F
F
MeO
OMe
F
F

1H NMR: 6e
OMe
OMe
OMe
MeO
MeO
OMe
OMe
MeO

1H NMR: 6f
OMe
OMe
OMe
MeO
MeO
MeO
OMe
OH

13C NMR: 6f
OMe
OMe
OMe
MeO
MeO
OMe
OH
MeO

1H NMR: 6g
OMe
OMe
OMe
MeO
MeO
MeO
B(OH)2

13C NMR: 6g
OMe
OMe
OMe
MeO
MeO
MeO
B(OH)2

1H NMR: 6h
OMe
OMe
OMe
N
MeO
MeO
MeO