Organic Letters
Letter
330. (d) Snieckus, V. Chem. Rev. 1990, 90, 879. The OMe directed-
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1070.
(5) (a) Metal-Catalyzed Cross-Coupling Reactions, 2nd ed.; de Meijere,
A., Diederich, F., Eds.; Wiley-VCH: Weinheim, Germany, 2004. For
recent examples, see, inter alia: (b) Hupp, C. D.; Neumeyer, J. L.
Tetrahedron Lett. 2010, 51, 2359. (c) Behenna, D. C.; Stockdill, J. L.;
Stoltz, B. M. Angew. Chem., Int. Ed. 2007, 46, 4077. For the less
commonly used reductive groups (OMs, OTs, and others), see:
(d) Mori, A.; Mizusaki, T.; Ikawa, T.; Maegawa, T.; Monguchi, Y.;
Sajiki, H. Chem. - Eur. J. 2007, 13, 1432 and references cited therein.
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additional benefit of DreM/cyclization reactions to more highly
condensed aromatics;18,25 and (e) as insightfully pointed out by
Martin,11a the use of the hydrodemethoxylation process in late-
stage chemoselective C−OMe cleavage of pharmaceutically
relevant molecules.26
In summary, this work demonstrates new reactions of
potential general value based on the conceptual interplay of
classical (SEAr) and modern (DoM, cross-coupling) reactivity
whose further utility in the regioselective construction of
polysubstituted aromatics and heteroaromatics of natural
product and bioactive and materials molecules may be
anticipated.
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
(7) (a) Jørgensen, K. B.; Rantanen, T.; Dorfler, T.; Snieckus, V. J.
̈
Org. Chem. 2015, 80, 9410. (b) Sengupta, S.; Leite, M.; Raslan, D. S.;
Quesnelle, C.; Snieckus, V. J. Org. Chem. 1992, 57, 4066. Also see:
(c) Kinsman, A. C.; Snieckus, V. Tetrahedron Lett. 1999, 40, 2453. For
cleavage using a reductant under Ni catalysis, see: (d) Mesganaw, T.;
Fine Nathel, N. F.; Garg, N. K. Org. Lett. 2012, 14, 2918. Although
stoichiometric C−OMe reductions using alkali metals have been
reported, they are limited by harsh conditions and low efficiency. See:
(e) Azzena, U.; Dettori, G.; Idini, M. V.; Pisano, L.; Sechi, G.
Tetrahedron 2003, 59, 7961. (f) Casado, F.; Pisano, L.; Farriol, M.;
Gallardo, I.; Marquet, J.; Melloni, G. J. Org. Chem. 2000, 65, 322.
(g) Maercker, A. Angew. Chem., Int. Ed. Engl. 1987, 26, 972.
(8) The bond dissociation enthalpy is ΔH298 = 101 kcal/mol. See:
(a) Blanksby, S. J.; Ellison, G. B. Acc. Chem. Res. 2003, 36, 255. For a
method using a stoichiometric amount of a Rh complex, see: (b) van
der Boom, M. E.; Liou, S.-Y.; Ben-David, Y.; Shimon, L. J. W.;
Milstein, D. J. Am. Chem. Soc. 1998, 120, 6531.
Experimental procedures and analytical data for new
compounds and products (PDF)
AUTHOR INFORMATION
■
Corresponding Author
ORCID
Notes
The authors declare no competing financial interest.
(9) (a) Kakiuchi, F.; Usui, M.; Ueno, S.; Chatani, N.; Murai, S. J. Am.
Chem. Soc. 2004, 126, 2706. For recent work, see: (b) Kondo, H.;
Kochi, T.; Kakiuchi, F. Org. Lett. 2017, 19, 794.
ACKNOWLEDGMENTS
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We are grateful to NSERC Canada for support of our synthetic
programs via the Discovery Grant (DG) program. We thank
Professor M. A. J. Miah (Department of Chemistry, Rajshahi
University, Bangladesh) for perceptive assistance.
(10) Tobisu, M.; Shimasaki, T.; Chatani, N. Angew. Chem., Int. Ed.
2008, 47, 4866.
́
(11) (a) Alvarez-Bercedo, P.; Martin, R. J. Am. Chem. Soc. 2010, 132,
17352. For mechanistic studies, see: (b) Cornella, J.; Gom
E.; Martin, R. J. Am. Chem. Soc. 2013, 135, 1997.
́
ez-Bengoa,
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D
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