Journal of the American Chemical Society
Communication
Proc. Res. Devel. 2011, 15, 1236. (c) Moran, J.; Krische, M. J. Pure Appl.
Chem. 2012, 84, 1729.
(4) Geary, L. M.; Glasspoole, B. W.; Kim, M. M.; Krische, M. J. J. Am.
Chem. Soc. 2013, 135, 3796.
(5) For a general review on the topic of benzannulation, see: Kotha,
S.; Misra, S.; Halder, S. Tetrahedron 2008, 64, 10775.
phenolic protecting group. The resulting cycloadduct (not
shown) is converted to the benzannulated steroid 11 in 87%
yield via DMF-acetal-mediated DODH followed by exposure to
activated charcoal in the presence of air (eq 4).12
(6) As observed in other ruthenium(0)-catalyzed C−C couplings
developed in our laboratory, carboxylic acid cocatalysts enhance rate
and conversion. See the following for a detailed interpretation of the
carboxylic acid cocatalyst effect: (a) Yamaguchi, E.; Mowat, J.; Luong,
T.; Krische, M. J. Angew. Chem., Int. Ed. 2013, 52, 8428. See also:
(b) McInturff, E. L.; Mowat, J.; Waldeck, A. R.; Krische, M. J. J. Am.
Chem. Soc. 2013, 135, 17230.
(7) For related acid-catalyzed aromatizations via double dehydration,
see: (a) Tsang, W.-S.; Griffin, G. W.; Horning, M. G.; Stillwell, W. G. J.
Org. Chem. 1982, 47, 5339. (b) Bharat, R. B.; Bally, T.; Valente, A.;
Cyranski, M. K.; Dobrzycki, L.; Spain, S. M.; Rempała, P.; Chin, M. R.;
́
King, B. T. Angew. Chem., Int. Ed. 2010, 49, 399.
In summary, a new protocol for benzannulation based on
ruthenium(0)-catalyzed diol−diene [4+2] cycloaddition is
described. Employing diol and tetraol reactants, benzannulation
can be conducted efficiently in one- and two-directional modes,
respectively, as illustrated in the construction of substituted
fluoranthenes and acenes. Application of this methodology to
the direct modification of abundant renewable polyols such as
ethylene glycol, glycerol, and cellulose is underway.
(8) Formation of the metal−olefin π-complex should precede
oxidative coupling, and the stability of the late transition metal−olefin
π-complex decreases with increasing degree of olefin substitution:
(a) Cramer, R. J. Am. Chem. Soc. 1967, 89, 4621. (b) Jesse, A. C.;
Cordfunke, E. H. P.; Ouweltjes, W. Thermochim. Acta 1979, 30, 293.
(9) For selected examples of catalytic diol DODH to form olefins,
see: (a) Gable, K. P.; Juliette, J. J. J. J. Am. Chem. Soc. 1996, 118, 2625.
(b) Cook, G. K.; Andrews, M. A. J. Am. Chem. Soc. 1996, 118, 9448.
(c) Ziegler, J. E.; Zdilla, M. J.; Evans, A. J.; Abu-Omar, M. M. Inorg.
Chem. 2009, 48, 9998. (d) Vkuturi, S.; Chapman, G.; Ahmad, I.;
Nicholas, K. M. Inorg. Chem. 2010, 49, 4744. (e) Ahmad, I.; Chapman,
G.; Nicholas, K. M. Organometallics 2011, 30, 2810. (f) Chapman, G.;
Nicholas, K. M. Chem. Commun. 2013, 49, 8199.
(10) As described in the Supporting Information, the tetraketone
corresponding to tetraol 1c was prepared from acenaphthalene in two
steps using a combination of literature procedures. Reduction of the
tetraketone to form the tetraol 1c required use of NaBH(OAc)3, as use
of more reactive hydride sources (e.g., NaBH4, LiAlH4, LiBHEt3) led
to decomposition. Although 1,2-diketones are reported to undergo
reductive [4+2] cycloaddition, when using o-quinones the yields of
product were prohibitively low.
ASSOCIATED CONTENT
* Supporting Information
Experimental procedures and spectral data. This material is
■
S
AUTHOR INFORMATION
Corresponding Author
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
The Robert A. Welch Foundation (F-0038), the NSF (CHE-
1265504), and the Government of Canada’s Banting
Postdoctoral Fellowship Program (L.M.G.) are acknowledged
for partial support of this research.
(11) See Supporting Information for the synthesis of cyclohexane
tetraol 1d, octahydronaphthalene tetraol 1e, and tricyclic tetraol 1f.
(12) King, J. L.; Posner, B. A.; Mak, K. T.; Yang, N.-C. C. Tetrahedron
Lett. 1987, 28, 3919.
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