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ChemComm
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COMMUNICATION
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experiments reported here show the utility of this platform for the
synthesis of novel, sterically congested PAHs such as helicenes,
iptycenes and angularly fused acene derivatives.
Furthermore, the selective generation of one of the aryne moieties
from 2 and subsequent reaction with an appropriate partner allows
DOI: 10.1039/C6CC01214K
Chem. Soc., 2002, 124, 4512.
T. Sato, H. Niino, A. Yabe, J. Photochem. Photobiol. A, 2001, 145,
3.
10 C. S. LeHoullier, G. W. Gribble, J. Org. Chem., 1983, 48, 1682.
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straightforward access to
a new structurally complex 3-
phenanthryne precursor. Generation of this 5-phenyl-substituted 3-
phenanthryne with CsF led to the serendipitous discovery of a novel
intramolecular aryne trapping reaction.
13 G. Thanasis, K. Masato, J. Org. Chem., 1993, 58, 7158.
14 Measured as the dihedral angle defined by C(15)–C(15a)–
C(15c)–C(16) in 10 and C(12)–C(12a)–C(12c)–C(1) in 12. See ESI
for details.
15 We recently demonstrated the ability of some
bis(trimethylsilyl)aryl bistriflates to generate both formal aryne
triple bonds sequentially, allowing easy access to complex
polycyclic aryne precursors, see ref. 7.
16 V. D. Pogula, T. Wang, T. R. Hoye, Org. Lett., 2015, 17, 856
17 For reports on base-promoted sp2 C–H bond arylation involving
aryne intermediates, see: (a) G. B. Bajracharya, O. Daugulis, Org.
Lett., 2008, 10, 4625 (intramolecular C–arylation of phenols); (b)
T. Truong, O. Daugulis, J. Am. Chem. Soc., 2011, 133, 4243
(intermolecular arylation of heteroarenes and arenes containing
acidic C–H bonds).
18 Solvent effects for acetonitrile were computed using the CPCM
model: (a) M. Cossi, N. Rega, G. Scalmani, V. Barone, J. Comp.
Chem., 2003, 24, 669; (b) V. Barone M. Cossi, J. Phys. Chem. A,
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Acknowledgements
Financial support from the Spanish Ministry of Economy and
Competitiveness (MINECO, CTQ2013-44142-P and MAT2013-46593-
C6-6-P), the European Union (Project PAMS, contract no. 610446),
Xunta de Galicia (GPC2014/25) and FEDER is gratefully
acknowledged. We also thank the Centro de Supercomputación de
Galicia (CESGA) for generous allocation of computer time.
Notes and references
‡
Electronic supplementary information (ESI) available:
Experimental, spectroscopic and computational CCDC 1443038
and 1443039. DOI: .
§
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General reviews on aryne chemistry: (a) Hoffmann, R. W.
Dehydrobenzene and Cycloalkynes, Academic Press, New York,
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19 The calculated spin density map of the open shell singlet 21
supports a σ-π diradical character, showing separation of the pi-
type density, delocalized in the upper ring and a sigma-type
density localized on the sp2 hybrid orbital at C(8).
2
(a) R. Stoerme and B. Kahlert, Ber. Dtsch. Chem. Ges., 1902, 35,
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Kobayashi, H. Naito, T. Komatsu, Chem.–Eur. J., 2010, 16, 890;
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