annulation through the Diels–Alder reaction, followed by two-
ring construction through nickel-catalysed reaction of the diyne
moiety with acetylene, gave tricyclic compound 8.11 Similarly,
Diels–Alder reaction of dienediyne 1b and 1c derived from a
phenylethynylstannane gave 9a and 9b,12 and 9a was further
converted into tetracyclic compound 10 through zirconocene-
mediated reaction with o-diiodobenzene.13 Alternatively, 1b
was first transformed by zirconocene-mediated cyclization to
tetraene 11, which underwent double Diels–Alder reaction with
diethyl acetylenedicarboxylate to give tricyclic compound
12.14
In addition to the homocoupling reaction, alkynylstannyla-
tion products can naturally be applied also to the palladium-
catalysed cross-coupling reaction with various organic hal-
ides.15 Actually, iodobenzene, vinyl bromide and
1-bromo-2-phenylethyne reacted with 5b to give various
alkynylmethyl substituted conjugated compounds (Scheme 5).
Notes and references
1 H. Hopf, Classics in Hydrocarbon Chemistry, Wiley-VCH, Weinheim,
2000, pp. 423–426.
2 K. Krohn, Angew. Chem., Int. Ed. Engl., 1986, 25, 790–807.
3 (a) E. Shirakawa, H. Yoshida, T. Kurahashi, Y. Nakao and T. Hiyama,
J. Am. Chem. Soc., 1998, 120, 2975–2976; (b) E. Shirakawa, K.
Yamasaki, H. Yoshida and T. Hiyama, J. Am. Chem. Soc., 1999, 121,
10221–10222; (c) H. Yoshida, E. Shirakawa, T. Kurahashi, Y. Nakao
and T. Hiyama, Organometallics, 2000, 19, 5671–5678.
4 E. Shirakawa, H. Yoshida, Y. Nakao and T. Hiyama, J. Am. Chem. Soc.,
1999, 121, 4290–4291; H. Yoshida, E. Shirakawa, Y. Nakao, Y. Honda
and T. Hiyama, Bull. Chem. Soc. Jpn., 2001, 74, 637–647.
5 E. Shirakawa, H. Yoshida, Y. Nakao and T. Hiyama, Org. Lett., 2000,
2, 2209–2211.
6 E. Shirakawa, Y. Nakao and T. Hiyama, Chem. Commun., 2001,
263–264.
7 The palladium-catalysed three component coupling of 1,2-dienes,
distannanes and organic iodides has been reported to give allylstannanes
as net carbostannylation products of 1,2-dienes: F. Y. Yang, M. Y. Wu
and C. H. Cheng, Tetrahedron Lett., 1999, 40, 6055–6058.
8 Although the reaction mechanism is not clear at present, it may follow
the catalytic cycle of the acylstannylation of 1,2-dienes, which should
start with oxidative addition of a carbon–tin bond to a nickel(0)
complex. See reference 6.
9 (a) X. Han, B. M. Stoltz and E. J. Corey, J. Am. Chem. Soc., 1999, 121,
7600–7605; (b) E. Shirakawa, Y. Murota, Y. Nakao and T. Hiyama,
Synlett, 1997, 1143–1144; (c) J. P. Parrish, V. L. Flanders, R. J. Floyd
and K. W. Jung, Tetrahedron Lett., 2001, 42, 7729–7731, and references
cited therein.
10 The synthesis of 1d from 2,3-bis(bromomethyl)-1,3-butadiene and
cyclization utilizing the diene moiety but not the diyne moiety has been
reported: Y. Gaoni and S. Sadeh, J. Org. Chem., 1980, 45, 870–881.
11 Y. Sato, T. Nishimata and M. Mori, J. Org. Chem., 1994, 59,
6133–6135.
12 The homocoupling reaction of a mixture of dl and meso 1c gave the
corresponding diastereomeric mixture of 9b.
13 T. Takahashi, R. Hara, Y. Nishihara and M. Kotora, J. Am. Chem. Soc.,
1996, 118, 5154–5155.
14 The double Diels–Alder reaction of 1,2,4,5-tetramethylenecyclohexane
has been reported: W. J. Bailey, E. J. Fetter and J. Economy, J. Org.
Chem., 1962, 27, 3479–3482; D. T. Longone and F.-P. Boettcher, J. Am.
Chem. Soc., 1963, 85, 3436–3443.
15 For a review of the palladium-catalysed coupling of organostannanes
with organic electrophiles, see: K. Fugami and M. Kosugi, Top. Curr.
Chem., 2002, 219, 87–130; Acceleration of the coupling reaction by
cuprous chloride, see reference 9a.
Scheme 5 Reagents and conditions: i, Ph–I (1.0 equiv.), LiCl (1.5 equiv.),
Pd(PPh3)4 (5 mol %), CuCl (1.0 equiv.), DMSO, 50 °C, 4.5 h, 87%; ii,
CH2 = CH–Br (3.0 equiv.), LiCl (1.5 equiv.), Pd2(dba)3 (2.6 mol %), CuCl
(1.0 equiv.), DMSO–THF, 50 °C, 19 h, 47%; iii, Ph–CM C–Br (1.3 equiv.),
LiCl (1.5 equiv.), Pd(PPh3)4 (5 mol %), CuCl (1.0 equiv.), DMSO, 50 °C,
4 h, 83%.
In conclusion, we have demonstrated that dienediynes 1,
readily available from the alkynylstannylation products of
1,2-dienes, are versatile precursors for polycyclic compounds
having linearly-fused six-membered rings. Further studies on
details of synthetic applications are in progress in our
laboratories.
E. S. thanks the Asahi Glass Foundation and the Ministry of
Education, Sports, Culture, Science, and Technology, Japan
Government, for Grant-in-Aid for Scientific Research, No.
12750758 for financial support. T. H. is thanking the Ministry
of Education, Sports, Culture, Science, and Technology, Japan
Government, for Grant-in-Aid for COE Research on Elements
Science, No. 12CE2005.
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1963