products were further transformed into valuable benzoate and
phenol derivatives via palldium-catalyzed methoxycarbonylation
or oxidation with H O .
2
2
This research was partially supported by the Ministry of
Education, Science, Sports and Culture, Grant-in-Aid for Young
Scientists (A), 17685008. We gratefully acknowledge financial
support from the Tokuyama Science Foundation and Japan
Combinatorial Chemistry Focus Group Award in Synthetic
Organic Chemistry, Japan.
Scheme 4
Notes and references
{ Crystallographic data: Intensity data were collected at 173 K on a Bruker
˚
SMART APEX diffractometer with Mo Ka radiation (0.71073 A) and
graphite monochrometer. The structure was solved by direct methods and
2
refined by the full-matrix least-squares on F (SHELXTL). 4a [C18
H23BO
6
,
¯
Mw 5 346.17]; space group P1, triclinic; unit-cell dimensions a 5
˚
˚
˚
6
.0252(4) A, b 5 12.4955(9) A, c 5 13.2849(9) A, a 5 62.7990(10)u,
3
˚
b 5 84.221(2)u, c 5 84.2950(10)u, V 5 883.45(11) A ; Z 5 2, Dcalc
5
23
1
.301 g cm ; Total 6887 reflections were measured and 4645 were
independent [R(int) 5 0.0307]. Final R 5 0.0726, wR 5 0.2234 [I .
s(I)], and GOF 5 0.991 (for all data, R 5 0.0790, wR 5 0.2337). CCDC
71948. See http://dx.doi.org/10.1039/b506977g for crystallographic data in
CIF or other electronic format.
1
2
2
2
1
2
1
For reviews, see: N. Miyaura and A. Suzuki, Chem. Rev., 1995, 95,
457; A. Suzuki, J. Organomet. Chem., 1999, 576, 147; S. Kotha,
2
K. Lahiri and D. Kashinath, Tetrahedron, 2002, 58, 9633; F. Bellina,
A. Carpita and R. Rossi, Synthesis, 2004, 2419.
2
3
For reviews, see: T. Hayashi, Synlett, 2001, 879; T. Hayashi and
K. Yamazaki, Chem. Rev., 2003, 103, 2829.
N. A. Petasis, A. Goodman and I. A. Zavialov, Tetrahedron, 1997, 53,
1
1
6463; N. A. Petasis and I. A. Zavialov, J. Am. Chem. Soc., 1998, 120,
1798; N. A. Petasis and Z. D. Patel, Tetrahedron Lett., 2000, 41, 9607;
N. A. Petasis and S. Boral, Tetrahedron Lett., 2001, 42, 539.
Scheme 5
1
1
4 N. Miyaura and H. C. Brown, in Organic Synthesis via Boranes, Vol. 3,
Suzuki Coupling, Aldrich Chemical, Milwaukee, 2003, p. 5.
the Cp*RuCl-catalyzed cyclotrimerization. Consequently, the
cycloaddition of a,v-diynes with those alkynes has never been
accomplished under ruthenium-catalyzed conditions. On the other
hand, the cycloadduct of 3a and methyl propiolate was indirectly
obtained via the cycloaddition of 3a and 2 followed by the catalytic
methoxycarbonylation of resultant 4a (Scheme 5). Although the
catalytic alkoxycarbonylation of arylboronates has remained
5
T. Ishiyama, M. Murata and N. Miyaura, J. Org. Chem., 1995, 60,
7508; T. Ishiyama, Y. Itoh, T. Kitano and N. Miyaura, Tetrahedron
Lett., 1997, 38, 3447; T. Ishiyama, K. Ishida and N. Miyaura,
Tetrahedron, 2001, 57, 9813; M. Murata, S. Watanabe and Y. Masuda,
J. Org. Chem., 1997, 62, 6458; M. Murata, T. Oyama, S. Watanabe and
Y. Masuda, J. Org. Chem., 2000, 65, 164; D. M. Willis and
R. M. Strongin, Tetrahedron Lett., 2000, 41, 8683.
14
6
7
For a review, see: T. Ishiyama and N. Miyaura, J. Organomet. Chem.,
almost unexplored, we recently devised the new protocol to
2
003, 680, 3.
A. Maderna, H. Pritzkow and W. Siebert, Angew. Chem., Int. Ed. Engl.,
996, 35, 1501; C. Ester, A. Maderna, H. Pritzkow and W. Siebert, Eur.
synthesize phthalides by the catalytic carbonylation of boraphtha-
15
lides. Gratifingly, our protocol proved to be effective for 4a. The
treatment of 4a with 5 mol% Pd(OAc) , 11 mol% PPh , and
1
J. Inorg. Chem., 2000, 1177; Y. Gu, H. Pritzkow and W. Siebert, Eur. J.
Inorg. Chem., 2001, 373; A. Goswami, C.-J. Maier, H. Pritzkow and
W. Siebert, Eur. J. Inorg. Chem., 2004, 2635.
2
3
1
equiv of p-benzoquinone (BQ) in dry MeOH under CO
atmosphere at room temperature. The starting material was
completely consumed within 1.5 h to afford the desired benzoate
8
9
M. W. Davies, C. N. Johnson and J. P. A. Harrity, Chem. Commun.,
1999, 2107; M. W. Davies, C. N. Johnson and J. P. A. Harrity, J. Org.
Chem., 2001, 66, 3525; J. E. Moore, M. York and J. P. A. Harrity,
Synlett, 2005, 860.
Y. Yamamoto, J. Ishii, H. Nishiyama and K. Itoh, J. Am. Chem. Soc.,
2004, 126, 3712.
1
1 in 77% yield. Electron-rich alkoxyacetylenes are also incompa-
tible substrates for our ruthenium catalysis, although their
cycloadducts are valuable phenol derivatives. In contrast, the
oxidation of 4a with H
2
O
2
under basic conditions gave bicyclic
10 V. Gandon, D. Leca, T. Aechtner, K. P. C. Vollhardt, M. Malacria and
C. Aubert, Org. Lett., 2004, 6, 3405.
phenol 12 in 93% yield. These methods were further applied to
anthraquinone boronate 4h to deliver naturally occurring anthra-
16,17
quinone derivatives 13 and 14.
1
1 Y. Yamamoto, T. Arakawa, R. Ogawa and K. Itoh, J. Am. Chem. Soc.,
003, 125, 12143.
2 C. Blanchard, E. Framery and M. Vaultier, Synthesis, 1996, 45.
2
1
In conclusion, we realized for the first time the catalytic [2 + 2 +
13 K. Kirchner, M. J. Calhorda, R. Schmid and L. F. Veiros, J. Am. Chem.
Soc., 2003, 125, 11721.
2
] cycloaddition of a,v-diynes with an alkynylboronate by means
of the ruthenium catalysis. Consequently, the novel protocol
allowed us to prepare functionalized bi- or tricyclic arylboronates
via Cp*RuCl-catalyzed reaction of 2-ethynyl-5,5-dimethyl-1,3,2-
dioxaborinane with various 1,6- and 1,7-diynes. The present
protocol tolerates reactive functional groups including an ester, a
ketone, a nitrile, and a sulfonamide. The obtained arylboronate
1
4 N. Miyaura and A. Suzuki, Chem. Lett., 1981, 879; T. Ohe, K. Ohe,
S. Uemura and N. Sugita, J. Organomet. Chem., 1988, 344, C5;
C. S. Cho, T. Ohe and S. Uemura, J. Organomet. Chem., 1995, 496, 221.
1
5 Y. Yamamoto, J. Ishii, H. Nishiyama and K. Itoh, J. Am. Chem. Soc.,
005, 127, 9625.
6 M.-J. Liou, C.-M. Teng and T.-S. Wu, J. Chin. Chem. Soc., 2002, 49,
025.
2
1
1
17 A. R. Burnett and R. H. Thomson, Phytochemistry, 1968, 7, 1421.
4
440 | Chem. Commun., 2005, 4438–4440
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