Organometallics
ARTICLE
Grant-in-Aid for Scientific Research (19105002 and 22750090)
from the MEXT, Japan. Y.I. thanks the JSPS for a Research
Fellowship for Young Scientists.
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(14) The cyclopolymerization of 1,5- and 1,6-diynes that proceeds
through a metathesis mechanism has been reported; see: (a) Zhang, W.;
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(15) For examples of Bergman cyclopolymerization of bis-ortho-
diynyl arenes containing internal alkynes, see: (a) Shah, H. V.; Babb,
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(16) For examples of the asymmetric cyclopolymerization of an achiral
1,5-hexadiene in the presence of optically active Zirconium catalysts, see:
(a) Coates, G. W.; Waymouth, R. M. J. Am. Chem. Soc. 1991, 113, 6270.
(b) Coates, G. W.; Waymouth, R. M. J. Mol. Catal. 1992, 76, 189.
(c) Coates, G. W.; Waymouth, R. M. J. Am. Chem. Soc. 1993, 115, 91.
(d) Yeori., A; Goldberg, I.; Kol, M. Macromolecules 2007, 40, 8521.
(17) For examples of the asymmetric radical cyclopolymerization
of achiral unconjugated dienes in the presence of a stoichiometric
amount of chiral precatalysts, see: (a) Seno, M.; Kawamura, Y.; Sato,
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(18) We have reported the use of a rhodium/chiral diene catalyst for
catalytic asymmetric polymerization of achiral arylacetylenes. See ref 6.
(19) For reviews, see: (a) Shintani, R.; Hayashi, T. Aldrichim. Acta
2009, 42, 31. (b) Defieber, C.; Gr€utzmacher, H.; Carreira, E. M. Angew.
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(20) (a) Nishimura, T.; Yasuhara, Y.; Nagaosa, M.; Hayashi, T.
Tetrahedron: Asymmetry 2008, 19, 1778. (b) Nishimura, T.; Kumamoto,
H.; Nagaosa, M.; Hayashi, T. Chem. Commun. 2009, 5713. (c) Shintani,
R.; Takeda, M.; Nishimura, T.; Hayashi, T. Angew. Chem., Int. Ed. 2010,
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Chem. Soc. 2010, 132, 7872. (e) Nishimura, T.; Makino, H.; Nagaosa,
M.; Hayashi, T. J. Am. Chem. Soc. 2010, 132, 12865.
(21) For an example of rhodium-catalyzed cross alkyne cyclotrimer-
ization of 1,6-diynes and terminal acetylenes, see: Tanaka, K.; Nishida,
G.; Wada, A.; Noguchi, K. Angew. Chem., Int. Ed. 2004, 43, 6510.
(22) Saeed, I.; Shiotsuki, M.; Masuda, T. Macromolecules 2006,
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(23) For the details of time dependence of [R]D of polymers, see the
Supporting Information.
(24) A rhodium complex of tfb is known to be the most active
catalyst among those of conventional dienes in the polymerization of
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(26) For the details of preparation of 13C-labeled nitrogen-bridged
1,8-diyne (1d-13C), see the Supporting Information.
(27) The 13C NMR H3 and IR spectral data H3 of ethyl acetal 4b
(13C NMR: δ 15.4 (OCH2CH3), 60.3 (OCH2CH3), 105.8 (C acetal),
169.5 (CdO); IR: 1771 cmꢀ1 (CdO)) were found to agree with those
of a similar acetal reported previously; see: Genrich, F.; Harms, G.;
Schaumann, E.; Gjikaj, M.; Adiwidjaja, G. Tetrahedron 2009, 65, 5577.
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dx.doi.org/10.1021/om200088q |Organometallics 2011, 30, 2342–2348