attachment of the dienophile fragment. Moreover, 2-substi-
tuted 1,3-butadienes are an integral part of many natural
As a continuation of our work on developing new
13,14
methodologies using dimethylsulfonium methylide 4,
we
7
15
products. This has resulted in the development of a number
have recently reported an interesting observation that 4 in
combination with a base, such as sodium dimsylate, under-
goes a tandem ylide addition-eliminative olefination on
various activated olefins and thus acts as an equivalent of a
carbene anion. This strategy has been used in sequential
tandem olefination-alkylation for the preparation of 1-sub-
stituted vinyl silanes, styrenes, and products derived from
8-11
of methods for their preparation.
Many of these meth-
odologies involve organometallic species such as 1,3-
9
10
butadienyl-2-metal or 2,3-butadienyl-1-metal, which often
suffer from poor regioselectivity or low yield and, in some
cases, require starting materials that are not readily accessible.
More recently, attractive alternative methods such as Barbier-
8
,11c
11b,d
16
type coupling
and ethylene-alkyne cross-metathesis
them. The methodology has been extended for sequential
have been reported for their preparation. However, although
efficient, few methods are applicable to the synthesis of
tandem double olefination of vinyl phosphonates and alde-
hydes to provide di- and tri-substituted 1,3-dienes with very
17
2-substituted 1,3-butadienes where a quick assembly of a
high regio- and stereoselectivity. We were curious to know
whether this novel olefination is applicable to extended
conjugated systems such as 1,3-diendioates 1 and if so, which
of the two regioisomeric dienic products 2 or 3 (Scheme 2)
dienophile fragment can be made to perform T2IMDA.
We envisage that the nucleophilic addition of a carbene
1
2
anion equivalent to an activated 1,3-diene 1 (Scheme 2)
18
would dominate. Although, the conjugate addition of carbon
or heteroatomic nucleophilic reagents to activated olefins is
a highly useful reaction in organic synthesis, the regiose-
lectivity issue, namely, 1,4-addition versus 1,6-addition,1
sometimes becomes challenging to extended conjugated
systems. We report herein the first example of tandem 1,4-
addition-elimination of ylide 4 to 4-aryl/alkyl-substituted
Scheme 2
9-22
1
,3-diendioates 1 to give 1,3-butadien-2-ylmalonates 2, a
(
11) (a) Phukan, P.; Bauer, M.; Maier, M. E. Synthesis 2003, 1324-
1
(
(
328. (b) Smulik, J. A.; Diver, S. T. J. Org. Chem. 2000, 65, 1788-1792.
c) Lu, W.; Ma, J.; Yang, Y.; Chan, T. H. Org. Lett. 2000, 2, 3469-3471.
d) Smulik, J. A.; Diver, S. T. Org. Lett. 2000, 2, 2271-2274. (e) Katritsky,
A. R.; Serdyuk, L.; Toader, D.; Wang, X. J. Org. Chem. 1999, 64, 1888-
1
892. (f) Yu, C.-M.; Yoon, S.-K.; Lee, S.-J.; Lee, J.-Y.; Kim, S. Chem.
would provide a solution to this. Depending on the regio-
and stereoselectivity of the addition, four isomeric 2-substi-
tuted 1,3-diene products, E and Z 2, 3, can be formed.
Commun. 1998, 2749-2750.
(12) For the use of this terminology, see: Cohen, T.; Yu, L. C. J. Org.
Chem. 1984, 49, 605-608.
(13) Corey, E. J.; Chaykovsky, M. J. Am. Chem. Soc. 1965, 87, 1353-
1
364.
(
5) Selected examples of recent approaches to the bridgehead alkene,
(14) For other uses of 4, see: Alcaraz, L.; Cox, K.; Cridland, A. P.;
Kinchin, E.; Morris, J.; Thompson, S. P. Org. Lett. 2005, 7, 1399-1401
and references therein.
(15) (a) Date, S. M.; Singh, R.; Ghosh, S. K. Org. Biomol. Chem. 2005,
3, 3369-3378. (b) Ghosh, S. K.; Singh, R.; Date, S. M. Chem. Commun.
2003, 636-637.
(16) (a) Singh, R.; Singh, G. C.; Ghosh, S. K. Tetrahedron Lett. 2005,
46, 4719-4722. (b) Singh, R.; Singh, G. C.; Ghosh, S. K. Eur. J. Org.
Chem. 2007, 5376-5385. (c) Ghosh, S. K.; Singh, R.; Singh, G. C. Eur. J.
Org. Chem. 2004, 4141-4147.
(17) (a) Date, S. M.; Ghosh, S. K. Angew. Chem., Int. Ed. 2007, 46,
386-388. (b) Date, S. M.; Ghosh, S. K. Bull. Chem. Soc. Jpn. 2004, 77,
2099-2100.
(18) Reviews: (a) Lipshutz, B.H.; Sengupta, S. Organic Reactions;
Paquette, L. A., Ed.; John Wiley & Sons: New York, 1992; Vol. 41, pp
135-631. (b) Perlmutter, P. Conjugate Addition Reactions in Organic
Synthesis; Pergamon Press: Oxford, 1992.
see: (a) Mehta, G.; Kumaran, R. S. Chem. Commun. 2002, 1456-1457.
(
(
b) Sgarbi, P. W. M.; Clive, D. L. J. Chem. Commun. 1997, 2157-2158.
c) Sheehan, S. M.; Lalic, G.; Chen, J. S.; Shair, M. D. Angew. Chem., Int.
Ed. 2000, 39, 2714-2715. (d) Cossy, J.; BouzBouz, S.; Laghgar, M.;
Tabyaoui, B. Tetrahedron Lett. 2002, 43, 823-827. (e) Yoshimitsu, T.;
Yanagiya, M.; Nagaoka, H. Tetrahedron Lett. 1999, 40, 5215-5218. (f)
Yoshimitsu, T.; Yanagisawa, S.; Nagaoka, H. Org. Lett. 2000, 2, 3751-
3
(
4
754. (g) Njardarson, J. T.; Wood, J. L. Org. Lett. 2001, 3, 2431-2434.
h) Kaliappan, K. P.; Ravikumar, V.; Pujari, S. A. Tetrahedron Lett. 2006,
7, 981-984.
6) Reviews on anti-Bredt alkenes and their reactivities: (a) Shea, K. J.
(
Tetrahedron 1980, 36, 1683-1715. (b) Warner, P. M. Chem. ReV. 1989,
8
5
(
9, 1067-1093. (c) Marshall, J. A.; Faubl, H. J. Am. Chem. Soc. 1967, 89,
965-5966. (d) Wiseman, J. R. J. Am. Chem. Soc. 1967, 89, 5966-5968.
e) Wiseman, J. R.; Chong, J. A. J. Am. Chem. Soc. 1969, 91, 7775-7777.
(7) (a) Shen, Y.-C.; Wang, L.-T.; Wang, C.-H.; Khalil, A. T.; Guh, J.-
H. Chem. Pharm. Bull. 2004, 52, 108-110. (b) Prakash, C. V. S.; Hoch, J.
M.; Kingston, D. G. I. J. Nat. Prod. 2002, 65, 100-107. (c) Iwamoto, M.;
Ohtsu, H.; Tokuda, H.; Nishino, H.; Matsunaga, S.; Tanaka, R. Bioorg.
Chem. Lett. 2001, 9, 1911-1921.
(19) Selected examples of Cu catalyzed addition: (a) Yamamoto, Y.;
Yamamoto, S.; Yatagai, H.; Ishihara, Y.; Maruyama, K. J. Org. Chem. 1982,
47, 119-126. (b) Barbot, F.; Kadib-Elban, A.; Miginiac, P. Tetrahedron
Lett. 1983, 24, 5089-5090. (c) Corey, E. J.; Boaz, N. W. Tetrahedron Lett.
1985, 26, 6019-6022. (d) Barbot, F.; Kadib-Elban, A.; Miginiac, P. J.
Organomet. Chem. 1983, 255, 1-9. (e) Uerdingen, M.; Krause, N.
Tetrahedron 2000, 56, 2799-2804. (f) Liu, H.; Gayo, L. M.; Sullivan, R.
W.; Choi, A. Y. H.; Moore, H. W. J. Org. Chem. 1994, 59, 3284-3288.
(g) Modi, S. P.; Gardner, J. O.; Milowsky, A.; Wierzba, M.; Forgione, L.;
Mazur, P.; Solo, A. J.; Duax, W. L.; Galdecki, Z.; Grochulski, P.; Wawrzak,
Z. J. Org. Chem. 1989, 54, 2317-2321. (h) Krause, N.; Gerold, A. Angew.
Chem., Int. Ed. 1997, 36, 186-204.
(8) (a) Alcaide, B.; Almendros, P.; Rodr ´ı guez-Acebes, R. J. Org. Chem.
2
1
7
002, 67, 1925-1928. (b) Bloch, R.; Chaptal-Gradoz, N. J. Org. Chem.
994, 59, 4162-4169. (d) Patel, R. M.; Argade, N. P. J. Org. Chem. 2007,
2, 4900-4904. (e) Deagostino, A.; Prandi, C.; Zavattaro, C.; Venturello,
P. Eur. J. Org. Chem. 2006, 2463-2483. (f) Molander, G. A.; Yokoyama,
Y. J. Org. Chem. 2006, 71, 2493-2498 and references therein.
(9) (a) Luo, M.; Iwabuchi, Y.; Hatakeyama, S. Synlett 1999, 1109-1111.
(
b) Nativi, C.; Taddei, M. Tetrahedron 1989, 45, 1131-1144. (c) Brown,
P. A.; Jenkins, P. R. J. Chem. Soc., Perkin Trans. 1 1986, 1129-1131. (d)
Wada, E.; Kanemasa, S.; Fujiwara, I.; Tsuge, O. Bull. Chem. Soc. Jpn.
(20) Iron-catalyzed addition: (a) Fukuhara, K.; Urabe, H. Tetrahedron
Lett. 2005, 46, 603-606. (b) Furstner, A.; Martin, R. Chem. Lett. 2005,
34, 624-629.
1
985, 58, 1942-1945. (e) Nunomoto, S.; Yamahita, Y. J. Org. Chem. 1979,
I
4
4, 4788-4791.
(21) Rh -catalyzed addition: (a) Hayahi, T.; Yamamoto, S.; Tokugana,
(10) (a) Yu, C.-M.; Lee, S.-J.; Jeon, M. J. Chem. Soc., Perkin Trans. 1
N. Angew. Chem., Int. Ed. 2005, 44, 4224-4227. (b) Herran, G. de la;
Murcia, C.; Csaky, A. G. Org. Lett. 2005, 7, 5629-5632.
(22) Silicon and tin reagents: Krief, A.; Dumont, W.; Provins, L. Synlett
1995, 121-122.
1
999, 3557-3558. (b) Luo, M.; Iwabuchi, Y.; Hatakeyama, S. Chem.
Commun. 1999, 267-268. (c) Soundararajan, R.; Li, G.; Brown, H. C. J.
Org. Chem. 1996, 61, 100-104.
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