Moreover, butadiynes are of great interest in organic synthesis
as carbon-rich building blocks and also as key structural moieties
in the preparation of either intermediate in natural product
synthesis, in which the 1,3-butadiyne functional group undergoes
a transformation to another function5 or remains as such,6 or
complex cyclic frameworks.7
Bis(heterocumulenes) Derived from the
1,4-Diphenyl-1,3-butadiyne Framework. Synthesis
of Three New Classes of Axially Chiral
Biheteroaryls
Mateo Alajar´ın,*,† Baltasar Bonillo,† AÄ ngel Vidal,*,† and
Functionalized 2-alkynylanilines are accessible compounds
which have found recent applications in heterocyclic chemistry,
mainly as precursors of indoles. Thus, the metal-catalyzed
intramolecular hydroamination of 2-alkynylanilines represents
a useful synthesis of this class of heterocycles.8 2-Alkynyla-
nilines have been also converted by standard chemistry into
N-[2-(1-alkynyl)phenyl]ketenimines 1 [Y ) C(R)] and N-[2-
(1-alkynyl)phenyl]-N′-arylcarbodiimides 1 (Y ) N) which
proceed via thermal and photochemical biradical cyclization to
produce, respectively, benzocarbazoles 3 and quinindolines 4
(Scheme 1).9
Delia Bautista‡
Departamento de Qu´ımica Orga´nica, Facultad de Qu´ımica,
UniVersidad de Murcia, Campus de Espinardo, 30100 Murcia,
Spain, and SerVicio UniVersitario de InVestigacio´n Cient´ıfica,
UniVersidad de Murcia, Campus de Espinardo,
30100 Murcia, Spain
ReceiVed September 26, 2007
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(10) (a) Kurihara, T.; Michiya, F.; Tabei, H. Jpn. Kokai Tokkyo Koho
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(11) Saulnier, M. G.; Frennesson, D. B.; Deshpande, M. S.; Vyas, D.
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(12) For some examples, see: (a) Alajar´ın, M.; Vidal, A.; Ort´ın, M.-M.
Synthesis 2007, 590-596. (b) Alajar´ın, M.; Bonillo, B.; Ort´ın, M.-M.;
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Tetrahedron 2005, 61, 1531-1537. (g) Alajar´ın, M.; Vidal, A.; Tovar, F.;
Sa´nchez-Andrada, P. Tetrahedron Lett. 2002, 43, 6259-6261. (h) Coss´ıo,
F. P.; Arrieta, A.; Lecea, B.; Alajar´ın, M.; Vidal, A.; Tovar, F. J. Org.
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Bis(ketenimines) and bis(carbodiimides) derived from 1,4-
bis(2-aminophenyl)-1,3-butadiynes via two independent bi-
radical cyclizations provided, respectively, axially chiral
bis(benzocarbazoles) and bis(quinindolines). Mixed bihet-
eroaryls, consisting of benzocarbazole and quinindoline units,
have been also prepared by a slightly modified strategy.
Compounds containing conjugated 1,3-butadiyne structures
are somewhat amazingly found in nature.1 This structural motif
is also frequently encountered in acetylenic oligomers and
polymers,2 macrocycles,3 and supramolecular structures,4 some
of them with applications in the area of new molecular materials.
† Departamento de Qu´ımica Orga´nica.
‡ Servicio Universitario de Investigacio´n Cient´ıfica.
(1) For some examples, see: (a) Nakao, Y.; Uehara, T.; Matunaga, S.;
Fusetani, N.; van Soest, R. W. J. Nat. Prod. 2002, 65, 922-924. (b)
Faulkner, D. J. Nat. Prod. Rep. 2002, 19, 1-48. (c) Zhang, H.; Lu, Z.;
Tan, G. T.; Qiu, S.; Farnsworth, N. R.; Pezzuto, J. M.; Fong, H. S.
Tetrahedron Lett. 2002, 43, 973-977. (d) Zgoda, J. R.; Freyer, A. J.;
Killmer, L. B.; Porter, J. R. J. Nat. Prod. 2001, 64, 1348-1349. (e) Alam,
N.; Bae, B. H.; Hong, J.; Lee, C. O.; Im, K. W.; Jung, J. H. J. Nat. Prod.
2001, 64, 1059-1063. (f) Faulkner, D. J. Nat. Prod. Rep. 2001, 18, 1-49.
(g) Negishi, E.; Alimardanov, A.; Xu, C. Org. Lett. 2000, 2, 65-67. (h)
Youssef, D. T. A.; Yoshida, W. Y.; Kelly, M.; Scheuer, P. J. J. Nat. Prod.
2000, 63, 3320-3321.
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P. A.; Farinola, G. M.; Omar, O. H.; Naso, F. Chem. Commun. 2003, 130-
131. (b) Bunz, U. H. F.; Rubin, Y.; Yobe, Y. Chem. Soc. ReV. 1999, 107-
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(3) For some examples, see: (a) Hoger, S.; Enkelmann, V.; Bonrad, K.;
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M.; Ando, K.; Suzuki, T.; Tsuji, T. J. Org. Chem. 2000, 65, 4385-4390.
(c) Tobe, Y.; Fujii, T.; Matsumoto, H.; Tsumuraya, K.; Noguchi, D.;
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Am. Chem. Soc. 2000, 122, 1762-1775. (d) Eisler, S.; Tykwinski, R. R.
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10.1021/jo7021058 CCC: $40.75 © 2008 American Chemical Society
Published on Web 12/12/2007
J. Org. Chem. 2008, 73, 291-294
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