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COMMUNICATION
Journal Name
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The X-ray diffraction structures of adducts
8 and 21 showed
506.
(a) M. Rey-Carrizo, M. Barniol-XicotDaO, I:M10..1F0o39n/tC-B8CarCd0i3a1,88SF.
Vázquez, Angew. Chem. Int. Ed. 2014, 53, 8195; (b) P. Camps,
J. A. Fernández, S. Vázquez, M. Font-Bardia, X. Solans, Angew.
Chem. Int. Ed. 2003, 42, 4049; (c) P. Camps, X. Pujol, S.
that, for both compounds, the distances between the flagpole
hydrogen atoms (2.027 Å and 2.077 Å in and 21, respectively)
and the flagpole carbon atoms (2.620 Å and 2.615 Å in and 21
respectively) are smaller than the sum of the van der Waals
radius of the involved atoms (1.1–1.2 Å and 1.7–1.8 Å,
respectively). Thus, severe steric congestion should be expected
from the inability of the boat cyclohexane rings to relieve the
H–H and C–C flagpoles interactions. Notwithstanding, both
structures showed a high stability, remaining unaltered for
months at room temperature under air.
8
8
,
Vázquez, Org. Lett. 2000, 2, 4225.
5
6
(a) A. Nicolaides, J. M. Smith, A. Kumar, D. M. Barnhart, W. T.
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G. Johnson, W. T. Borden. Org. Lett. 2006, 8, 3001.
(a) R. W. Hoffmann. Dehydrobenzene and Cycloalkynes;
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Soc. Rev. 2012, 41, 3140–3152. (e) C. M. Gampe, E. M.
Carreira, Angew. Chem. Int. Ed. 2012, 51, 3766. (f) S. Yoshida,
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Soltz, Chem. Rev. 2012, 112, 3550. (h) D. Wu, H. Ge, J. Yin, RSC
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7
8
F. M. Logullo, A. H. Seitz, L. Friedman, Org. Synth, 1968, 48,
12.
For selected reviews, see: (a) A. M. Dyke, A. J. Hester, G. C.
Lloyd-Jones. Synthesis 2006, 4093. (b) M. A. Bennett, E.
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9
(a) Y. Himeshima, T. Sonoda, H. Kobayashi. Chem. Lett. 1983,
1211. (b) D. Peña, A. Cobas, D. Pérez, E. Guitián, L. Castedo,
Synthesis 2002, 1454.
8
21
Scheme 5. X-Ray diffraction structures for adducts
8
and 21.
10 (a) S. A. Worlikar, R. C. Larock, Curr. Org. Chem. 2011, 15
,
3214; (b) C. Romero, D. Peña, D. Pérez, E. Guitián, Chem. Eur.
J. 2006, 12, 5677; (c) E, Guitián, D. Pérez, D. Peña, Topics in
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Ed. 1998, 37, 2659.
In summary, a new cocyclotrimerization of arynes with a
pyramidalized alkene has been reported. Different conditions
and metal catalysts have been tested, finding that simultaneous
and parallel generation of arynes and pyramidalized alkenes in
the presence of Pd(PPh3)4, yielded the adducts resulting from
the reaction of two arynes with one alkene in good yields.
Notably, five different substituted or polycyclic arynes
successfully react with the pyramidalized alkene. This reaction
constitutes a first example of pyramidalized alkene reactivity
through palladium catalysis.
11 T. T. Jayanth, M. Jeganmohan, C.-H. Cheng. J. Org. Chem.
2004, 69, 8445.
12 I. Quintana, A. J. Boersma, D. Peña, D. Pérez, E. Guitián. Org.
Lett. 2006, 8, 3347.
13 N. Saito, K. Shiotani, A. Kinbara, Y. Sato. Chem. Commun.
2009, 4284.
14 For some recent examples, see: (a) D. Garcia, L. Rodriguez-
Pérez, M. A. Herranz, D. Peña, E. Guitián, S. Bailey, Q. Al-
Galiby, M. Noori, C. Lambert, D. Pérez, N. Martin. Chem.
Commun. 2016, 52, 6677; (b) I. Pozo, A. Cobas, D. Peña, E.
Guitián, D. Pérez, Chem. Commun. 2016, 52, 5534; (c) D.
Rodriguez-Lojo, D. Pérez, D. Peña, E. Guitián, Chem. Commun.
2015, 51, 5418; (d) A. Criado, M. Vizuete. M. J. Gomez-
Escalonilla, S. Garcia-Rodriguez, J. L. Fierro, A. Cobas, D. Peña,
E. Guitián, F. Langa, Carbon 2013, 63, 140; (e) D. Rodriguez-
Lojo, A. Cobas, D. Peña, D. Pérez, E. Guitián, Org. Lett. 2012,
14, 1363; (f) K. Z. Laczkowski, D. Garcia, D. Peña, A. Cobas, D.
Pérez, E. Guitián, Org. Lett. 2011, 13, 960.
Acknowledgements
The research leading to these results received funding from the
EU project PAMS (610446), the Agencia Estatal de Investigacion
(MAT2016-78293-C6-3-R and CTQ2016-78157-R), the Xunta de
Galicia (Centro singular de investigacion de Galicia, acreditacion
2016-2019, ED431G/09) and the European Regional
Development Fund (ERDF).
15 (a) M. A. Bennett, D. C. Hockles, E. Wenger, Organometallics,
1995, 14, 2091. (b) K. Shahlai, H. Hart, J. Org. Chem. 1989, 11
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Notes and references
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18 For preliminary attempts using two additional pyramidalized
alkenes see supporting information.
19 CCDC 1554197 (for compound 8), 1554198 (for compound
21).
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4 | J. Name., 2012, 00, 1-3
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