J . Org. Chem. 2000, 65, 7475-7478
7475
P a lla d iu m -Ca ta lyzed Cr oss-Cou p lin g of 3-Iod obu t-3-en oic Acid
w ith Or ga n om eta llic Rea gen ts. Syn th esis of 3-Su bstitu ted
Bu t-3-en oic Acid s
Mohamed Abarbri,† J ean-Luc Parrain,‡ Masato Kitamura,§ Ryoji Noyori,§ and
Alain Ducheˆne*,†
Laboratoire de Physicochimie des Interfaces et des Milieux Re´actionnels, Faculte´ des Sciences de Tours,
Parc de Grandmont, 37200 Tours, France, Laboratoire de Synthe`se Organique associe´ au CNRS, Case
postale D12, Faculte´ des Sciences de Saint J e´roˆme, Avenue Escadrille Normandie-Niemen, 13397
Marseille Cedex 20, France, and Department of Chemistry and Research Center for Materials Science,
Nagoya University, Chikusa, Nagoya 464-8602, J apan
duchene@delphi.phys.univ-tours.fr
Received May 17, 2000
3-Substituted but-3-enoic acids were obtained in good yields under mild experimental conditions
by palladium-catalyzed cross-coupling of 3-iodobut-3-enoic acid with organozinc or organotin
compounds using PdCl2(MeCN)2 as catalyst and DMF as solvent.
Sch em e 1
In tr od u ction
Intermediate compounds bearing two electrophilic
centers have been widely used over the past few years
as the key step in total synthesis.1 Some bi-electrophiles
containing a carboxylic function have proved to be
valuable in the synthesis of terpenoic acid deriva-
tives.2 The most widely used of the series of but-3-enoic
acid synthons is diketene whose opening by various
organometallics leads to 3-substituted but-3-enoic acids
(Scheme 1).3
quantities of 3-substituted but-3-enoic acids. We therefore
planned a new approach to this type of acids through the
reactions between 3-iodobut-3-enoic acid and various
organometallic compounds.
However, this process does not allow the satisfactory
introduction of vinylic and benzylic groups (especially in
terms of yields given by vinylic organometallics), owing
mainly to formation of polymers. Moreover, it is well-
known that diketene decomposes violently in the pres-
ence of a base.4 This is a limitation to obtaining high
Resu lts a n d Discu ssion
Syn th esis of 3-Iod obu t-3-en oic Acid . Hydroiodation
of the but-2,3-dienoic acid,5 initially prepared by carbo-
natation reaction of allenylmagnesium bromide with
hydroiodic acid, yielded only the nonconjugated 3-iodobut-
3-enoic acid (1) at room temperature.6 Increasing the
temperature led to a mixture of (1) and the E and Z
isomers of 3-iodobut-2-enoic acid.
* To whom correspondence should be addressed. Tel.: +33-2-47-
36-69-59. Fax: +33-2-47-36-70-40.
† Faculte´ des Sciences de Tours.
‡ Faculte´ des Sciences de Marseille.
Using an identical procedure, heating the but-3-ynoic
acid at 70 °C for 6 h yielded 69% of iodovinylic acid 1
without any isomerization product (Scheme 2).
§ Nagoya University.
(1) (a) Comprehensive Organic Synthesis; Trost, B. M., Fleming, I.,
Ed.; Pergamon Press: Oxford, 1991; Vol. 4, pp 865-906. (b) Nozaki,
H. Organometallics in Synthesis; Schlosser, M., Ed.; J ohn Wiley: New
York, 1994; Chapter 8, pp 535-578.
Rea ctivity of 3-Iod obu t-3-en oic Acid . The reactivity
of iodovinylic acid 1 was then studied through the
substitution of the iodine atom.7 The substitution reaction
of 1 was carried out with various organometallic re-
agents. Preliminary experiments with Grignard reagents
or organocuprates in various solvents (such as ether,
THF, and HMPA) did not allow the expected substitution.
On the basis of Negishi’s work,8 we decided to use
organozinc reagents under palladium(II) catalysis in THF
which provided poor yields of a mixture of the 3-substi-
(2) See, for example, the following. Synthesis of ipsdienone or
ipsenone: (a) Silverstein, R. M.; Rodin, J . O.; Wood, D. L. Science 1966,
154, 509. (b) Reece, C. A.; Rodin, J . O.; Brownlee, R. G.; Duncan, W.
G.; Silverstein, R. M. Tetrahedron 1968, 24, 4249. (c) Tokuda, M.;
Mimura, N.; Karasawa, T.; Fujita, H.; Suginome, H. Tetrahedron Lett.
1993, 34, 7607. (d) Mori, K.; Takigawa, T.; Matsuo, T. Tetrahedron
1978, 35, 933. Synthesis of citral a: (e) Ohtsuru, M.; Teraoka, M.; Tori,
K.; Takeda, K. J . Chem. Soc. 1967, 1035. Synthesis of γ-geranic acid:
(f) Cardillo, G.; Contento, M.; Sandri, S. Tetrahedron Lett. 1974, 25,
2215. (g) Bedoukian, R. H.; Wolinsky, J . J . Org. Chem. 1975, 40, 2154.
(3) (a) Trost, B. M. Acc. Chem. Res. 1978, 11, 453. (b) Trost, B. M.;
Brandi, A. J . Org. Chem. 1983, 49, 4811 and references given therein.
(c) Itoh, K.; Fukui, M.; Kurachi, Y. J . Chem. Soc., Chem. Commun.
1977, 500. (d) Itoh, K.; Yogo, T.; Ishii, Y. Chem. Lett. 1977, 103. (e)
Fujisawa, T.; Sato, T.; Gotoh, Y.; Kawashima, M.; Kawara, T. Bull.
Chem. Soc. J pn. 1982, 55, 3555. (f) Abe, Y.; Sato, M.; Goto, H.;
Sugawara, R.; Takahashi, E.; Kato, T. Chem. Pharm. Bull. 1983, 31,
4346. (g) Yamamoto, K.; Ikeda, K.; Yin, L. K. J . Organomet. Chem.
1989, 370, 319. (h) Itoh, K.; Harada, T.; Nagashima, H. Bull. Chem.
Soc. J pn. 1991, 64, 3746.
(5) (a) Wotiz, J . H. J . Am. Chem. Soc. 1950, 26, 1639. (b) Prevost,
C.; Gaudemar, M.; Honiberg, J . Compt. Rend. Acad. Sci. 1950, 230,
1186. (c) J ones, E. R. H.; Whitham, G. H.; Whiting, M. C. J . Chem.
Soc. 1954, 3201.
(6) Chalcat, J . C.; The´ron, F.; Vessie`re, R. Compt. Rend. Acad. Sci.
Ser. C 1971, 273, 763.
(4) Perrins, D. D.; Armarego, W. L. F. Purification of Laboratory
Chemicals, 4th ed.; Butterworth Publishers: New York, 1996.
(7) Ducheˆne, A.; Abarbri, M.; Parrain, J . L.; Kitamura, M.; Noyori,
R. Synlett 1994, 524.
10.1021/jo0007579 CCC: $19.00 © 2000 American Chemical Society
Published on Web 09/29/2000