ORGANIC
LETTERS
2002
Vol. 4, No. 9
1491-1493
A New Reaction of Aryl Aldehydes with
Aryl Acetylenes in the Presence of
Boron Trihalides†
George W. Kabalka,* Zhongzhi Wu, and Yuhong Ju
Departments of Chemistry and Radiology, The UniVersity of Tennessee,
KnoxVille, Tennessee 37996-1600
Received February 8, 2002
ABSTRACT
The reactions of aryl aldehydes with 2 equiv of arylacetylenes in the presence of boron trichloride yield (E,Z)-1,3,5-triaryl-1,5-dichloro-1,4-
pentadienes. Reactions carried out in the presence of boron tribromide generate the corresponding (Z,Z)-1,3,5-triaryl-1,5-dibromo-1,4-pentadienes.
Vinylboranes are versatile reagents in organic synthesis.1
They are utilized in transformations such as Diels-Alder
reactions,2 additions to carbonyl compounds,3 and a variety
of coupling reactions which generate new carbon-carbon
skeletons.4 Vinylboranes are generally prepared via hydro-
boration of alkynes with boron hydrides5 or the haloboration
of 1-alkynes.6 Haloboration reactions and their applications
in organic chemistry have been extensively reviewed.7 The
reactions usually occur in a stereo-, regio-, and chemo-
selective fashion via the syn addition of the B-X moiety to
(4) (a) Rivera, I.; Soderquist, J. A. Tetrahedron Lett. 1991, 32, 2311.
(b) Miyaura, N.; Yamada, K.; Suginome, H.; Suzuki, A. J. Am. Chem. Soc.
1985, 107, 972. (c) Yang, D. W.; Huang, X. J. Organomet. Chem. 1997,
543, 165. (d) Nishi, K.; Narukawa, Y.; Onoue, H. Tetrahedron Lett. 1996,
37, 2987. (e) Brown, H. C.; Basavaiah, D. J. Org. Chem. 1982, 47, 3806.
(f) Periasamy, M.; Prasad, A. S. B.; Susseela Y. Tetrahedron 1995, 51,
2743. (g) Ishiyama, T.; Nishijima, K.; Miyaura, N.; Suzuki, A. J. Am. Chem.
Soc. 1993, 115, 7219. (h) Negishi, E.; Yoshida, T.; Abramovitch, A.; Lew,
G.; Williams, R. M. Tetrahedron 1991, 47, 343. (i) Suzuki, A. Pure Appl.
Chem. 1991, 63, 419. (j) Brown, H. C.; Molander, G. A. J. Org. Chem.
1981, 46, 645.
(5) (a) Brown, H. C.; Zaidlewicz, M. Chem. Stosow. 1982, 26, 155. (b)
Soundararajan, R.; Matteson, D. S. J. Org. Chem. 1990, 55, 2274. (c) Tucker,
C. E.; Davidson, J.; Knochel, P. J. Org. Chem. 1992, 57, 3482. (d) Brown,
H. C.; Scouten, C. G.; Liotta, R. J. Am. Chem. Soc. 1979, 101, 96. (e)
Soderquist, J. A.; Colberg, J. C.; Del Valle, L. J. Am. Chem. Soc. 1989,
111, 4873. (f) Lane, C. F.; Kabalka, G. W. Tetrahedron 1976, 32, 981. (g)
Gridnev, I. D.; Miyaura, N.; Suzuki, A. Organometallics 1993, 12, 589.
(h) Brown, H. C.; Basavaiah, D. J. Org. Chem. 1982, 47, 754. (i) Brown,
H. C.; Campbell, J. B., Jr. J. Org. Chem. 1980, 45, 389, (j) Brown, H. C.;
Basavaiah, D.; Kulkarni, S. U. J. Org. Chem. 1982, 47, 3808. (k) Brown,
H. C.; Imai, T. Organometallics 1984, 3, 1392.
† This paper is dedicated to Professor Herbert C. Brown, a pioneer in
organoborane chemistry, on the occasion of his 90th birthday.
(1) (a) Pelter, A.; Smith, K.; Brown, H. C. Boron Reagents; Academic
Press: San Diego, CA, 1988. (b) Brown, H. C. Organic Syntheses Via
Borane; John Wiley & Sons: New York, 1975. (c) Larock, R. C.
ComprehensiVe Organic Transformations; VCH: New York, 1989. (d)
Brown, H. C.; Ramachandran, P. V. Spec. Publ.-R. Soc. Chem. 1997, 201,
151. (e) Wrackmeyer, B. Spec. Publ.-R. Soc. Chem. 1997, 201, 73.
(2) (a) Singleton, D. A. AdV. Cycloaddition 1997, 4, 121. (b) Seitz, G.;
Haenel, F. Arch. Pharm. 1994, 327, 673. (c) Singleton, D. A.; Redman, A.
M. Tetrahedron Lett. 1994, 35, 509. (d) Singleton, D. A.; Martinez, J. P.;
Watson, J. V.; Ndip, G. M. Tetrahedron 1992, 48, 5831. (e) Singleton, D.
A.; Martinez, J. P.; Ndip, G. M. J. Org. Chem. 1992, 57, 5768. (f) Batey,
R. A.; Lin, D.; Wong, A.; Hayhoe, C. L. S. Tetrahedron Lett. 1997, 38,
3699. (g) Singleton, D. A.; Kim, K. I.; Martinez, J. P. Tetrahedron Lett.
1993, 34, 3071.
(3) (a) Jacob, P., III; Brown, H. C. J. Org. Chem. 1977, 42, 579. (b)
Rane, A. M.; Vaquer, J.; Colberg, J. C.; Soderquist, J. A. Tetrahedron Lett.
1995, 36, 987. (c) Mikhailov, B. M.; Shchegoleva, T. A. IzV. Akad. Nauk.
SSSR. Ser. Khim. 1971, 661. (d) Takaya, Y.; Ogasawara, M.; Hayashi, T.
Tetrahedron Lett. 1998, 39, 8479. (e) Yanagi, T.; Sasaki, H.; Suzuki, A.;
Miyaura, N. Synth. Commun. 1996, 26, 2503. (f) Fujita, K.; Schlosser, M.
HelV. Chim. Acta 1982, 65, 1258.
(6) (a) Lappert M. F.; Prokai, B. J. Organomet. Chem. 1964, 1, 384. (b)
Blackborow, J. R. J. Organomet. Chem. 1977, 128, 161. (c) Satoh, Y.;
Tayano, T.; Koshino, H.; Hara, S.; Suzuki, A. Synthesis 1985, 406. (d)
Blackborow, J. R. J. Chem. Soc., Perkin Trans. 2 1973, 1989.
(7) (a) Suzuki, A. Pure Appl. Chem. 1986, 58, 829. (b) Suzuki, A. ReV.
Heteroat. Chem. 1997, 17, 271. (c) Suzuki, A. Hara, S. Trends Org. Chem.
1990, 1, 77.
10.1021/ol025696a CCC: $22.00 © 2002 American Chemical Society
Published on Web 04/06/2002