Synthesis of biaryl compounds using tandem ruthenium-catalyzed ring-closing metathesis

Article abstract of DOI:10.1002/chem.201002074

Tandem ring-closing enyne metathesis (RCEM)/ring-closing olefin metathesis (RCM) of tetraenynes with Grubbs second-generation catalyst, followed by elimination, was found to be a new and efficient synthetic approach to biaryl compounds. A preliminary asymmetric version of this approach, which used homochiral Ru-alkylidene catalysts, is also presented. A ringing endorsement: Tandem ring-closing enyne metathesis (RCEM)/ring-closing olefin metathesis (RCM) of tetraenynes with the Grubbs second-generation catalyst followed by elimination, was found to be a new and efficient synthetic approach to biaryl compounds (see scheme). A preliminary asymmetric version of this approach is also presented.

Full text of DOI:10.1002/chem.201002074

DOI: 10.1002/chem.201002074
Synthesis of Biaryl Compounds Using Tandem Ruthenium-Catalyzed Ring-
Closing Metathesis
Kazuhiro Yoshida,* Hiroaki Shida, Hidetoshi Takahashi, and Akira Yanagisawa*[a]
Abstract: Tandem ring-closing enyne metathesis (RCEM)/ring-closing olefin meta-
thesis (RCM) of tetraenynes with Grubbs second-generation catalyst, followed by
elimination, was found to be a new and efficient synthetic approach to biaryl com-
pounds. A preliminary asymmetric version of this approach, which used homochi-
ral Ru–alkylidene catalysts, is also presented.
Keywords: aromatic compounds ·
asymmetric synthesis · metathesis ·
ring closure · synthesis design
Introduction
and the ring-closing enyne metathesis[7] (RCEM)/dehydra-
tion of 1,5-octadien-7-yn-4-ols 3 [Eq. (2)],[6j] respectively. On
the basis of those studies, we report here a new synthetic
Modern synthetic organic chemistry has sufficient flexibility
to construct acyclic compounds selectively. Therefore, the
construction of aromatic rings from acyclic precursors is an
attractive approach to obtain substituted aromatic com-
pounds without the formation of inseparable regioisomers.[1]
Recently, a considerable number of studies have been con-
ducted on the synthesis of aromatic compounds by using
ruthenium-catalyzed ring-closing olefin metathesis[2,3]
(RCM).[4,5] The reason for this is clearly the great reliability
of RCM as a cyclization reaction. In the past few years, we
have focused our efforts on this field[6] and reported that
substituted benzenes 2 and styrenes 4 can be synthesized by
the RCM/dehydration of 1,5,7-octatrien-4-ols 1 [Eq. (1)][6e]
strategy that yields biaryl compounds 6 from tetraenynes 5,
in which two rings are consecutively constructed by the
RCEM/RCM/elimination sequence[8] (Scheme 1).[9]
Scheme 1. Synthesis of biaryl compounds 6 by tandem RCEM/RCM/de-
hydration of 5.
[a] Prof. Dr. K. Yoshida, H. Shida, Dr. H. Takahashi,
Prof. Dr. A. Yanagisawa
Department of Chemistry, Graduate School of Science
Chiba University, Yayoi-cho
Inage-ku, Chiba 263-8522 (Japan)
Fax : (+81)43-290-2789
E-mail: kyoshida@faculty.chiba-u.jp
ayanagi@faculty.chiba-u.jp
Results and Discussion
Our retrosynthetic analysis of substrates 5 is outlined in
Scheme 2. First, we prepared dienynedials 7 by the Sonoga-
shira coupling between two well-known building blocks, b-
halo-a,b-unsaturated aldehydes 8[10] and 2-penten-4-ynal 9.
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201002074.
344
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 344 – 349

FULL PAPER
product 6b was obtained in a higher yield than that of 5a
(entry 3 vs. 1). The reaction of 5c with ethyl groups at the
R4 and R4’ positions also proceeded to give 6c in 79% yield
(entry 4). On the other hand, the synthesis of 6d that has
methyl groups at the R2 and R2’ positions was unsuccessful.
The cyclization of 5d did not occur at all (entry 5). Whereas
the reaction of fluorine-containing substrate 5e proceeded
to give 6e in moderate yield (entry 6), the reaction of 5 f
gave bibenzothiophene 6 f in high yield (entry 7). The intro-
duction of ester groups at R3 and R3’ positions was also ac-
complished, but slow cyclization gave rise to low yields (en-
tries 8 and 9). One surprising result was that substrate 5h is
unreactive in this system (entry 10). Considering the prob-
lem-free synthesis of analogous product 6a (entry 1), the
cyclization seemed to have suffered seriously from steric in-
teractions between the two methoxy groups at the 7- and 7’-
positions of 6h. In conformity with this view, the synthesis
of nonsymmetrically substituted
Scheme 2. Retrosynthetic analysis of substrates 5.
Then, we carried out double allylation of resulting coupling
products 7 to furnish desired substrates 5.[11]
We first surveyed the reaction conditions for the synthesis
of 1,1’-binaphthyl compound 6a from 5a that was chosen as
the model substrate (Table 1). To our delight, when RCEM/
RCM of 5a with 2.5 mol% Grubbs second-generation cata-
biaryl compound 6i, the struc-
ture of which is the same as
that of 6h except for the hydro-
gen at 7’-position, proceeded
Table 1. Survey of reaction conditions for synthesis of 1,1’-binaphthyl compound 6a.[a]
without
any
problems
(entry 11). The reactions of 5j
and 5k produced nonsymmetri-
cally substituted biaryl com-
Entry
10 [mol%]
Atmosphere
t [h]
Yield [%][b] pounds 6j and 6k, respectively
(entries 12 and 13). Although
the reaction of 5l with a methyl
ester group at the R3 position
was slightly slow as predicted,
6l was obtained in higher yields
than 6g (entries 8 and 9 vs. 14
and 15). Difficulties arose in
the cyclization of 5m and 5n
with a substituent at the R2 po-
sition, and corresponding prod-
1
2
3
4
5
6
2.5
2.5
5.0
7.5
15
C2H4
C2H4
C2H4
C2H4
C2H4
N2
2
4
2
2
2
2
36
39
61
74
87
53
7.5
[a] Ring-closing metathesis was carried out with 5a and ruthenium catalyst 10 in toluene at 808C. The reaction
mixture was treated with p-toluenesulfonic acid (15 mol%) at RT for 1 h. [b] Isolated yield by silica gel chro-
matography.
lyst 10[12] under an ethylene atmosphere[6j,13] at 808C for 2 h,
followed by dehydration with a catalytic amount of p-tolu-
ACHTUNGTRENNUNGenesulfonic acid, was carried out, desired 6a was obtained,
ucts 6m and 6n were not isolated at all (entries 16 and 17).
However, the reaction of 5o exceptionally gave 6o in spite
of possession of a methyl group at the R2 position (en-
tries 18 and 19). The last example is the formation of 1-aryl-
naphthalene. Despite the slow reaction and the low yield,
desired product 6p was isolated (entry 20).
We next examined the application of the method to asym-
metric synthesis (Scheme 3). When the reaction of 5o was
carried out with homochiral Ru–alkylidene catalyst 11,[14]
although the conversion was low (Table 1, entry 1). Even
though we prolonged the reaction time to 4 h, no significant
improvement was observed in terms of product yield
(entry 2). As the catalyst decomposition is likely responsible
for the low conversion, we next examined the influence of
catalyst loading. We were pleased to see that the product
yield gradually increased with increasing catalyst loading
(entries 3–5). Although the reaction also proceeded under a
nitrogen atmosphere, the yield was lower than that under an
ethylene atmosphere (entry 4 vs. 6).
With these basic data, we examined the generality of the
synthetic approach to biaryl compounds. Examples of the
synthesis of symmetrically substituted biaryl compounds and
nonsymmetrically substituted biaryl compounds are listed in
entries 1–10 and entries 11–20 in Table 2, respectively. The
reaction of 5b that has no methyl groups at the R3 and R3’
positions with 10 (7.5 mol%) proceeded well and desired
Scheme 3. Asymmetric synthesis of 1,1’-binaphthyl compound 6o using
homochiral Ru–alkylidene catalyst 11.
Chem. Eur. J. 2011, 17, 344 – 349
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
345

K. Yoshida, A. Yanagisawa et al.
Table 2. Synthesis of biaryl compounds 6 by tandem RCEM/RCM/dehydration of 5.[a]
Entry Substrate
Product
Conditions[b]
Yield Entry Substrate
[%][c]
Product
Conditions[b]
Yield
[%][c]
1
10 (7.5 mol%) 74
10 (15 mol%) 87
10 (7.5 mol%) 85
11
12
13
10 (7.5 mol%)
90
76
77
2
3
10 (7.5 mol%)
10 (7.5 mol%)
4
10 (7.5 mol%) 79
14
10 (7.5 mol%)
41
5
6
10 (7.5 mol%)
0
15
16
10 (15 mol%)
10 (7.5 mol%)
64
10 (7.5 mol%) 54
0
7
10 (7.5 mol%) 88
17
10 (7.5 mol%)
10 (7.5 mol%)
0
8
9
10 (7.5 mol%)
7
18
19
67
10 (15 mol%) 25
10 (7.5 mol%)[d] 41
346
www.chemeurj.org
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 344 – 349

Biaryl Compounds
FULL PAPER
Table 2. (Continued)
Entry Substrate
Product
Conditions[b]
Yield Entry Substrate
[%][c]
Product
Conditions[b]
Yield
[%][c]
10
10 (7.5 mol%)
0
20
10 (7.5 mol%)
16
[a] Ring-closing metathesis was carried out with 5 and ruthenium catalyst 10 in toluene for 2 h. The reaction mixture was treated with p-toluenesulfonic
acid (15 mol%) at RT for 1 h. [b] Reactions were carried out at 808C. [c] Isolated yield by silica gel chromatography. [d] Reaction carried out at RT.
Experimental Section
8% ee of (R)-6o was obtained in 14% yield. Despite the in-
sufficient result, this preliminary investigation demonstrates
the possibility of applying RCM to the asymmetric synthesis
General: All anaerobic and moisture-sensitive manipulations were car-
ried out with standard Schlenk techniques under predried nitrogen or
of axial chiral biaryl compounds.
glovebox techniques under prepurified argon. NMR spectra were record-
ed using a JEOL JNM LA-500 spectrometer (500 MHz for 1H and
125 MHz for 13C), an ECA-500 spectrometer (500 MHz for 1H and
125 MHz for 13C), an LA-400 spectrometer (400 MHz for 1H and
100 MHz for 13C), and an ECS-400 spectrometer (400 MHz for 1H and
100 MHz for 13C) at the Chemical Analysis Center, Chiba University.
Chemical shifts are reported in d [ppm] referenced to an internal SiMe4
Finally, we applied this method to the synthesis of 2,2’-
and 1,2’-binaphthyl compounds (Scheme 4). As a result,
newly prepared substrates 12 and 14 were successfully con-
verted into desired products 13 and 15 by the RCEM/RCM/
elimination sequence, respectively.[15]
1
standard for H NMR spectroscopy and [D]chloroform (d=77.0 ppm) for
13C NMR spectroscopy. High-resolution mass spectra were recorded
using Thermo Fisher Scientific Exactive Orbitrap mass spectrometers at
the Chemical Analysis Center, Chiba University. Optical rotations were
measured using a JASCO P-1020 polarimeter. In the HRMS data, APCI
stands for atmospheric pressure chemical ionization.
Materials: Toluene was distilled with sodium benzophenone ketyl under
nitrogen and stored in a glass flask with a Teflon stopcock under nitro-
gen. Ruthenium complexes 10[12b] and 11[14] were prepared according to
the reported procedures. p-Toluenesulfonic acid monohydrate was used
as received.
General procedure for the preparation of biaryl compounds 6, 13, or 15:
Catalyst 10 (7.5 or 15 mol%) was added in one portion to a solution of 5,
12, or 14 in toluene (0.01m), which was then filled with ethylene gas in
three cycles. The reaction mixture was heated to 808C and stirred for 2 h
under the ethylene atmosphere. After cooling to room temperature, the
reaction mixture was treated with p-toluenesulfonic acid monohydrate
(15 mol%) and stirred for 1 h at room temperature. The mixture was
concentrated under reduced pressure and purified by silica gel column
chromatography or preparative thin-layer chromatography (PTLC) on
silica gel to afford 6, 13, or 15.
Scheme 4. Synthesis of 2,2’-binaphthyl compound 13 and 1,2’-binaphthyl
compound 15 by tandem RCEM/RCM/elimination of 12 and 14, respec-
tively.
7,7’-Dimethyl-5,5’-binaphthoACTHNUGRTENNUG[2,3-d]ACHTUNTGREN[NUGN 1,3]dioxole (6a): Compound 5a
(28.7 mg, 0.0662 mmol), 10 (8.4 mg, 0.00993 mmol), and toluene (6.6 mL)
were used. The crude mixture was purified by silica gel column chroma-
tography (chloroform/hexane=2:1) to afford 6a (21.4 mg, 87%). M.p.
Conclusion
1
290–2918C; H NMR (CDCl3): d=2.49 (s, 6H), 5.92 (s, 4H), 6.60 (s, 2H),
7.11 (s, 2H), 7.14 (s, 2H), 7.51 ppm (s, 2H); 13C NMR (CDCl3): d=21.37,
100.83, 102.71, 103.46, 126.12, 127.72, 128.23, 130.91, 133.47, 137.82,
147.06, 147.43 ppm; HRMS (ESI): m/z: calcd for C24H19O4: 371.1278 [M+
+H]; found: 371.1267.
In conclusion, we have developed a new synthetic approach
to biaryl compounds by utilizing the RCEM/RCM/dehydra-
tion sequence. The method employed for the synthesis of
biaryl compounds is remarkably different from the conven-
tional method represented by the cross-coupling reaction.
Although the method was found to be strongly dependent
on the substituents of the substrates when Grubbs second-
generation catalyst was used, we believe that future devel-
opment of active catalysts would increase the potential of
this method.
5,5’-BinaphthoACTHNUTRGENNGU[2,3-d]ACHTUNTGREN[NUGN 1,3]dioxole (6b): Compound 5b (55.4 mg,
0.136 mmol), 10 (8.7 mg, 0.0102 mmol), and toluene (13.6 mL) were used.
The crude mixture was purified by silica gel column chromatography
(chloroform/hexane=2:3) to afford 6b (39.5 mg, 85%). M.p. 261–2648C;
1H NMR (CDCl3): d=5.95 (s, 4H), 6.63 (s, 2H), 7.20 (s, 2H), 7.30 (d, J=
7.0 Hz, 2H), 7.42 (dd, J=7.7, 7.3 Hz, 4H), 7.74 ppm (d, J=8.3 Hz, 2H);
13C NMR (CDCl3): d=100.99, 102.83, 104.04, 124.03, 126.27, 126.87,
129.78, 130.75, 137.97, 147.47, 147.79 ppm; HRMS (APCI): m/z: calcd for
C22H14O4: 342.0887 [M+]; found: 342.0879.
Chem. Eur. J. 2011, 17, 344 – 349
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
347

K. Yoshida, A. Yanagisawa et al.
4,4’-Diethyl-1,1’-binaphthyl (6c): Compound 5c (58.8 mg, 0.157 mmol),
10 (10.0 mg, 0.0118 mmol), and toluene (15.7 mL) were used. The crude
mixture was purified by silica gel column chromatography (chloroform/
hexane=1:2) to afford 6c (38.3 mg, 79%). The 1H and 13C NMR spectra
were consistent with those reported previously.[16]
hexane=1:1) to afford 6l (22.4 mg, 64%). M.p. 146–1518C; 1H NMR
(CDCl3): d=3.97 (s, 3H), 7.26–7.35 (m, 2H), 7.36–7.44 (m, 2H), 7.45–
7.50 (m, 2H), 7.50–7.56 (m, 1H), 7.59 (dd, J=8.1, 7.2 Hz, 1H), 7.96 (t,
J=9.2 Hz, 2H), 8.06 (d, J=8.3 Hz, 1H), 8.10 (d, J=1.5 Hz, 1H),
8.72 ppm (s, 1H); 13C NMR (CDCl3): d=52.27, 125.39, 125.92, 126.16,
126.32, 126.61, 126.63, 127.02, 127.05, 127.91, 128.25, 128.39, 129.68,
130.94, 132.68, 132.75, 133.56, 135.06, 137.60, 139.00, 167.26 ppm; HRMS
(APCI): m/z: calcd for C22H17O2: 313.1223 [M++H]; found: 313.1211.
6,6’-Difluoro-3,3’-dimethyl-1,1’-binaphthyl (6e): Compound 5e (95.9 mg,
0.251 mmol), 10 (16.0 mg, 0.0188 mmol), and toluene (25.1 mL) were
used. The crude mixture was purified by silica gel column chromatogra-
phy (hexane/EtOAc=15:1) to afford 6e (42.7 mg, 54%). 1H NMR
(CDCl3): d=2.67 (s, 6H), 6.98 (td, J=8.7, 2.4 Hz, 2H), 7.22–7.33 (m,
4H), 7.44 (dd, J=9.8, 2.5 Hz, 2H), 7.63 ppm (s, 2H); 13C NMR (CDCl3):
d=21.64, 110.43 (d, J=20.1 Hz), 115.35 (d, J=25.1 Hz), 126.34 (d, J=
5.0 Hz), 128.08, 128.79 (d, J=9.0 Hz), 129.23 (d, J=3.0 Hz), 134.72 (d,
J=9.0 Hz), 136.33, 138.19, 160.73 ppm (d, J=245.5 Hz); HRMS (FAB):
m/z: calcd for C22H16F2: 318.1220 [M+]; found: 318.1213.
2-Methyl-1,1’-binaphthyl (6o): Compound 5o (48.1 mg, 0.145 mmol), 10
(9.3 mg, 0.0109 mmol), and toluene (14.5 mL) were used. The crude mix-
ture was purified by silica gel column chromatography (chloroform/
1
hexane=1:2) to afford 6o (25.8 mg, 67%). The H and 13C NMR spectra
were consistent with those reported previously.[18] The reaction was also
carried out with 5o (30.0 mg, 0.0902 mmol), homochiral Ru–alkylidene
catalyst 11a (6.8 mg, 0.00677 mmol, 7.5 mol%), and toluene (9.0 mL,
0.01m) at 208C for 24 h. The crude mixture was purified by PTLC on
silica gel (chloroform/hexane=1:2) to afford (R)-6o (3.3 mg, 14%,
8% ee). [a]2D0 =À6.09 (c=0.250, CHCl3);[19] HPLC (Daicel Chiralcel OJ);
hexane/EtOH/MeOH=1000:5:3.5, 1.0 mLminÀ1; tR (R)=7.6 min, tR (S)=
11.8 min.[20]
4,4’-Bibenzo[b]thiophene (6 f): Compound 5 f (75.9 mg, 0.230 mmol), 10
(14.6 mg, 0.0173 mmol), and toluene (23.0 mL) were used. The crude
mixture was purified by silica gel column chromatography (hexane/
EtOAc=10:1) to afford 6 f (53.6 mg, 88%). 1H NMR (CDCl3): d=7.07
(dd, J=5.7, 0.8 Hz, 2H), 7.34 (d, J=5.5 Hz, 2H), 7.38–7.44 (m, 4H),
7.92 ppm (ddd, J=7.0, 2.1, 0.6 Hz, 2H); 13C NMR (CDCl3): d=121.91,
123.74, 124.23, 125.42, 126.18, 136.42, 138.57, 140.23 ppm; HRMS
(APCI): m/z: calcd for C16H11S2: 267.0297 [M++H]; found: 267.0289.
1-(2-Cyclopropylphenyl)-6,7-dimethoxynaphthalene (6p): Compound 5p
(257 mg, 0.697 mmol), 10 (44.4 mg, 0.0523 mmol), and toluene (69.7 mL)
were used. The crude mixture was purified by silica gel column chroma-
tography (hexane/EtOAc=4:1) to afford 6p (34.5 mg, 16%). 1H NMR
(CDCl3): d=0.54–0.63 (m, 4H), 1.40–1.48 (m, 1H), 3.76 (s, 3H), 4.01 (s,
3H), 6.87 (s, 1H), 6.92 (d, J=7.7 Hz, 1H), 7.18 (s, 1H), 7.23–7.26 (m,
2H), 7.29 (dd, J=7.2, 0.9 Hz, 1H), 7.34 (ddd, J=8.4, 5.0, 3.7 Hz, 1H),
7.40 (dd, J=8.2, 6.9 Hz, 1H), 7.69 ppm (d, J=7.9 Hz, 1H); 13C NMR
(CDCl3): d=9.56, 9.79, 13.12, 55.59, 55.80, 77.20, 105.31, 106.46, 122.51,
123.83, 125.08, 125.68, 125.74, 127.73, 128.01, 129.24, 130.24, 138.26,
140.63, 142.20, 149.28 ppm; HRMS (ESI): m/z: calcd for C21H21O2:
305.1536 [M++H]; found: 305.1526.
Dimethyl 1,1’-binaphthyl-3,3’-dicarboxylate (6g): Compound 5g (31.6 mg,
0.0727 mmol), 10 (9.3 mg, 0.0109 mmol), and toluene (7.3 mL) were used.
The crude mixture was purified by PTLC on silica gel (chloroform only)
to afford 6g (6.8 mg, 25%); known compound.[17] 1H NMR (CDCl3): d=
3.98 (s, 6H), 7.36 (d, J=8.0 Hz, 2H), 7.39–7.43 (m, 2H), 7.55 (td, J=7.9,
1.3 Hz, 2H), 8.07 (d, J=8.3 Hz, 2H), 8.10 (s, 2H), 8.74 (s, 2H) ppm.
6,6’,7-Trimethoxy-3,3’-dimethyl-1,1’-binaphthyl (6i): Compound 5i
(82.1 mg, 0.188 mmol), 10 (12.0 mg, 0.0141 mmol), and toluene (18.8 mL)
were used; The crude mixture was purified by silica gel column chroma-
tography (hexane/EtOAc=4:1) to afford 6i (62.9 mg, 90%). 1H NMR
(CDCl3): d=2.51 (s, 3H), 2.54 (s, 3H), 3.52 (s, 3H), 3.91 (s, 3H), 4.00 (s,
3H), 6.65 (s, 1H), 6.89 (dd, J=9.2, 2.5 Hz, 1H), 7.12 (s, 1H), 7.14 (d, J=
2.4 Hz, 1H), 7.18 (d, J=1.9 Hz, 1H), 7.20 (d, J=1.5 Hz, 1H), 7.29 (d, J=
9.2 Hz, 1H), 7.55 (s, 1H), 7.59 ppm (s, 1H); 13C NMR (CDCl3): d=21.46,
21.68, 55.21, 55.56, 55.78, 105.30, 105.48, 105.97, 117.45, 125.40, 125.75,
126.24, 126.41, 127.71, 128.07, 128.31, 129.63, 133.26, 135.08, 135.68,
137.08, 138.65, 148.73, 149.41, 157.55 ppm; HRMS (APCI): m/z: calcd for
C25H25O3: 373.1798 [M++H]; found: 373.1784.
2,2’-Binaphthalene (13): Compound 12b (32.8 mg, 0.0815 mmol), 10
(5.2 mg, 0.00611 mmol), and toluene (8.2 mL) were used. The crude mix-
ture was purified by silica gel column chromatography (dichloromethane/
hexane=1:4) to afford 13 (17.1 mg, 82%). The 1H and 13C NMR spectra
were consistent with those reported previously.[21]
7-Methyl-5-(naphthalen-2-yl)naphthoACTHNUGRTNENUG[2,3-d]ACHTUNGTRENN[UGN 1,3]dioxole (15): Compound
14b (21.5 mg, 0.0467 mmol), 10 (3.0 mg, 0.00350 mmol), and toluene
(4.7 mL) were used. The crude mixture was purified by PTLC on silica
gel (dichloromethane/hexane=1:2) to afford 15 (10.8 mg, 74%). M.p.
1
190–1928C; H NMR (CDCl3): d=2.50 (s, 3H), 5.97 (s, 2H), 7.11 (s, 1H),
3-Methyl-1,1’-binaphthyl (6j): Compound 5j (50.9 mg, 0.153 mmol), 10
(9.7 mg, 0.0115 mmol), and toluene (15.3 mL) were used. The crude mix-
ture was purified by PTLC on silica gel (hexane/EtOAc=10:1) to afford
6j (31.0 mg, 76%). M.p. 120–1248C; 1H NMR (CDCl3): d=2.55 (s, 3H),
7.19 (t, J=7.6 Hz, 1H), 7.27 (t, J=7.6 Hz, 1H), 7.32 (d, J=7.6 Hz, 2H),
7.36–7.50 (m, 4H), 7.56 (t, J=7.5 Hz, 1H), 7.70 (s, 1H), 7.83 (d, J=
8.3 Hz, 1H), 7.92 ppm (d, J=7.9H, 2H); 13C NMR (CDCl3): d=21.65,
125.07, 125.35, 125.75, 125.83, 125.92, 126.34, 126.59, 126.82, 127.47,
127.74, 127.80, 128.11, 130.06, 131.14, 132.84, 133.49, 133.77, 134.92,
138.29, 138.51 ppm; HRMS (APCI): m/z: calcd for C21H17: 269.1325
7.15 (s, 1H), 7.21 (s, 1H), 7.46–7.60 (m, 4H), 7.84–7.96 ppm (m, 4H);
13C NMR (CDCl3): d=21.37, 100.93, 102.30, 103.63, 125.96, 126.12,
126.24, 126.77, 127.70, 128.02, 128.28, 128.44, 131.22, 132.49, 133.40,
133.49, 138.68, 139.21, 147.28, 147.41 ppm; HRMS (APCI): m/z: calcd for
C22H17O2: 313.1223 [M++H]; found: 313.1218.
ACHTUNGTRENNUNG
Acknowledgements
ACHUTNGRENNU[G 1,2-d]ACHUTNTGREN[NUGN 1,3]dioxole (6k): Com-
pound 5k (72.3 mg, 0.171 mmol), 10 (10.9 mg, 0.0128 mmol), and toluene
(17.1 mL) were used. The crude mixture was purified by silica gel column
chromatography (hexane/EtOAc=2:1) to afford 6k (47.5 mg, 77%).
M.p. 110–1158C; 1H NMR (CDCl3): d=3.54 (s, 3H), 4.01 (s, 3H), 6.18
(dd, J=8.6, 1.5 Hz, 2H), 6.67 (s, 1H), 6.99 (d, J=17.4 Hz, 1H), 7.01 (d,
J=17.4 Hz, 1H), 7.20 (s, 1H), 7.29–7.37 (m, 2H), 7.42 (dd, J=8.3,
7.3 Hz, 1H), 7.54 (dd, J=8.5, 7.0 Hz, 1H), 7.77 (d, J=8.3 Hz, 1H),
7.90 ppm (d, J=8.3 Hz, 1H); 13C NMR (CDCl3): d=55.55, 55.81, 101.67,
105.13, 106.45, 110.16, 119.38, 120.12, 120.82, 123.79, 125.82, 126.16,
126.26, 128.29, 129.13, 129.42, 137.06, 139.35, 141.28, 143.07, 149.39,
149.41 ppm; HRMS (APCI): m/z: calcd for C23H19O4: 359.1278 [M++H];
found: 359.1265.
We appreciate the financial support from a Grant-in-Aid for Scientific
Research, the Ministry of Education, Culture, Sports, Science and Tech-
nology, Japan.
[1] For examples, see: a) R. L. Danheiser, S. K. Gee, J. Org. Chem.
1984, 49, 1672–1674; b) P. Turnbull, H. W. Moore, J. Org. Chem.
1995, 60, 644–649; c) T. Takahashi, Z. Xi, A. Yamazaki, Y. Liu, K.
Nakajima, M. Kotora, J. Am. Chem. Soc. 1998, 120, 1672–1680;
d) K. H. Dçtz, P. Tomuschat, Chem. Soc. Rev. 1999, 28, 187–198;
e) A. R. Katritzky, J. Li, L. Xie, Tetrahedron 1999, 55, 8263–8293;
f) S. Saito, Y. Yamamoto, Chem. Rev. 2000, 100, 2901–2915; g) D.
Suzuki, H. Urabe, F. Sato, J. Am. Chem. Soc. 2001, 123, 7925–7926;
h) C. B. de Koning, A. L. Rousseau, W. A. L. van Otterlo, Tetrahe-
dron 2003, 59, 7–36; i) Y. Yamamoto, T. Arakawa, R. Ogawa, K.
Methyl 1,1’-binaphthyl-3-carboxylate (6l): Compound 5l (42.5 mg,
0.113 mmol), 10 (14.4 mg, 0.0169 mmol), and toluene (11.3 mL) were
used. The crude mixture was purified by PTLC on silica gel (chloroform/
348
www.chemeurj.org
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 344 – 349

Biaryl Compounds
FULL PAPER
Itoh, J. Am. Chem. Soc. 2003, 125, 12143–12160; j) T. Shibata, T.
Fujimoto, K. Yokota, K. Takagi, J. Am. Chem. Soc. 2004, 126, 8382–
8383; k) X. Bi, D. Dong, Q. Liu, W. Pan, L. Zhao, B. Li, J. Am.
Chem. Soc. 2005, 127, 4578–4579; l) N. Asao, Synlett 2006, 1645–
1656; m) K. Tanaka, T. Osaka, K. Noguchi, M. Hirano, Org. Lett.
2007, 9, 1307–1310; n) S. Serra, C. Fuganti, E. Brenna, Chem. Eur.
J. 2007, 13, 6782–6791; o) M. Gayral, J. M. Brown, Synlett 2007,
2823–2826.
[7] a) M. Mori, Top. Organomet. Chem. 1999, 1, 133–154; b) C. S. Poul-
sen, R. Madsen, Synthesis 2003, 1–18; c) S. T. Diver, A. J. Giessert,
Chem. Rev. 2004, 104, 1317–1382; d) M. Mori, Adv. Synth. Catal.
2007, 349, 121–135.
[8] Nolan and co-workers reported an interesting view of the mecha-
nism of ruthenium-catalyzed metathesis of dienyne. See: H. Clavier,
A. Correa, E. C. Escudero-Adꢂn, J. Benet-Buchholz, L. Cavallo,
S. P. Nolan, Chem. Eur. J. 2009, 15, 10244–10254.
[2] For a comprehensive review, see: a) Handbook of Metathesis (Ed.:
R. H. Grubbs), Wiley-VCH, Weinheim, 2003. For reviews, see:
b) R. H. Grubbs, S. Chang, Tetrahedron 1998, 54, 4413–4450; c) A.
Fꢁrstner, Angew. Chem. 2000, 112, 3140–3172; Angew. Chem. Int.
Ed. 2000, 39, 3012–3043; d) T. M. Trnka, R. H. Grubbs, Acc. Chem.
Res. 2001, 34, 18–29; e) A. H. Hoveyda, A. R. Zhugralin, Nature
2007, 450, 243–251.
[3] For reports on the pharmaceutical application of RCM on a multiki-
logram scale (>400 kg of cyclized product), see: a) T. Nicola, M.
Brenner, K. Donsbach, P. Kreye, Org. Process Res. Dev. 2005, 9,
513–515; b) N. K. Yee, V. Farina, I. N. Houpis, N. Haddad, R. P.
Frutos, F. Gallou, X.-J. Wang, X. Wei, R. D. Simpson, X. Feng, V.
Fuchs, Y. Xu, J. Tan, L. Zhang, J. Xu, L. L. Smith-Keenan, J. Vitous,
M. D. Ridges, E. M. Spinelli, M. Johnson, K. Donsbach, T. Nicola,
M. Brenner, E. Winter, P. Kreye, W. Samstag, J. Org. Chem. 2006,
71, 7133–7145; c) Y. S. Tsantrizos, J.-M. Ferland, A. McClory, M.
Poirier, V. Farina, N. K. Yee, X.-j. Wang, N. Haddad, X. Wei, J. Xu,
L. Zhang, J. Organomet. Chem. 2006, 691, 5163–5171.
[4] For reviews, see: a) T. J. Donohoe, A. J. Orr, M. Bingham, Angew.
Chem. 2006, 118, 2730–2736; Angew. Chem. Int. Ed. 2006, 45, 2664–
2670; b) W. A. L. van Otterlo, C. B. de Koning, Chem. Rev. 2009,
109, 3743–3782.
[5] For recent examples, see: a) T. J. Donohoe, J. F. Bower, J. A. Basut-
to, L. P. Fishlock, P. A. Procopiou, C. K. A. Callens, Tetrahedron
2009, 65, 8969–8980; b) T. J. Donohoe, J. F. Bower, Proc. Natl.
Acad. Sci. USA 2010, 107, 3373–3376.
[9] We have reported the first synthetic example of nonsymmetrically
substituted 1,1’-binaphthyl compound in our previous paper. See ref-
erence [6j].
[10] For a review, see: S. Brahma, J. K. Ray, Tetrahedron 2008, 64, 2883–
2896.
[11] See the Supporting Information for details of the synthesis of 5.
[12] a) M. Scholl, S. Ding, C. W. Lee, R. H. Grubbs, Org. Lett. 1999, 1,
953–956; b) T. M. Trnka, J. P. Morgan, M. S. Sanford, T. E. Wilhelm,
M. Scholl, T.-L. Choi, S. Ding, M. W. Day, R. H. Grubbs, J. Am.
Chem. Soc. 2003, 125, 2546–2558; c) G. C. Vougioukalakis, R. H.
Grubbs, Chem. Rev. 2010, 110, 1746–1787.
[13] Mori and co-workers reported the beneficial effects of ethylene at-
mosphere in RCEM. See: a) M. Mori, N. Sakakibara, A. Kinoshita,
J. Org. Chem. 1998, 63, 6082–6083. For recent examples of RCEM
conducted under ethylene gas atmosphere, see: b) B. G. Kim, M. L.
Snapper, J. Am. Chem. Soc. 2006, 128, 52–53; c) K. P. Kaliappan, V.
Ravikumar, J. Org. Chem. 2007, 72, 6116–6126; d) Q. Yang, Y.-Y.
Lai, W.-J. Xiao, H. Alper, Tetrahedron Lett. 2008, 49, 7334–7336.
[14] T. J. Seiders, D. W. Ward, R. H. Grubbs, Org. Lett. 2001, 3, 3225–
3228.
[15] In these cases, acyl protection of the free hydroxyl groups of the
substrates at the propargyl position was critical for the high yields.
A similar propensity was observed in our previous styrene synthesis.
See reference [6f].
[16] M. Kidowaki, M. Moriyama, M. Wada, N. Tamaoki, J. Phys. Chem.
B 2003, 107, 12054–12061.
[6] a) K. Yoshida, T. Imamoto, J. Am. Chem. Soc. 2005, 127, 10470–
10471; b) K. Yoshida, F. Kawagoe, N. Iwadate, H. Takahashi, T. Im-
amoto, Chem. Asian J. 2006, 1, 611–613; c) K. Yoshida, S. Horiuchi,
N. Iwadate, F. Kawagoe, T. Imamoto, Synlett 2007, 1561–1564; d) K.
Yoshida, T. Toyoshima, T. Imamoto, Chem. Commun. 2007, 3774–
3776; e) K. Yoshida, H. Takahashi, T. Imamoto, Chem. Eur. J. 2008,
14, 8246–8261; f) K. Yoshida, Y. Shishikura, H. Takahashi, T. Ima-
moto, Org. Lett. 2008, 10, 2777–2780; g) K. Yoshida, R. Narui, T.
Imamoto, Chem. Eur. J. 2008, 14, 9706–9713; h) K. Yoshida, T.
Toyoshima, T. Imamoto, Bull. Chem. Soc. Jpn. 2008, 81, 1512–1517;
i) K. Yoshida, F. Kawagoe, K. Hayashi, S. Horiuchi, T. Imamoto, A.
Yanagisawa, Org. Lett. 2009, 11, 515–518; j) H. Takahashi, K. Yoshi-
da, A. Yanagisawa, J. Org. Chem. 2009, 74, 3632–3640.
[17] S. Escudero, D. Pꢃrez, E. Guitiꢂn, L. Castedo, Tetrahedron Lett.
1997, 38, 5375–5378.
[18] C. Wolf, H. Xu, J. Org. Chem. 2008, 73, 162–167.
[19] T. Hayashi, K. Hayashizaki, T. Kiyoi, Y. Ito, J. Am. Chem. Soc.
1988, 110, 8153–8156.
[20] R. P. J. Bronger, P. J. Guiry, Tetrahedron: Asymmetry 2007, 18, 1094–
1102.
[21] N. Kirai, Y. Yamamoto, Eur. J. Org. Chem. 2009, 1864–1867.
Received: July 21, 2010
Published online: November 30, 2010
Chem. Eur. J. 2011, 17, 344 – 349
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
349