Organic Letters
Letter
Rappoport, Z., Liebman, J. F., Marek, I., Eds.; John Wiley & Sons, Ltd.:
Chichester, U.K., 2013.
ASSOCIATED CONTENT
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S
* Supporting Information
(12) (a) Review: Su, Y.; Jiao, N. Synthesis 2011, 11, 1678−1690.
(b) Hamze, A.; Brion, J.-D.; Alami, M. Org. Lett. 2012, 14, 2782−2785.
(c) Zeng, J.; Tan, Y. J.; Leow, M. L.; Liu, X.-W. Org. Lett. 2012, 14,
4386−4389. (d) Shirakawa, E.; Ikeda, D.; Masui, S.; Yoshida, M.;
Hayashi, T J. Am. Chem. Soc. 2012, 134, 272−279. (e) Taillefer, M.;
Xia, N.; Ouali, A. Angew. Chem., Int. Ed. 2007, 46, 934−936.
(13) For a recent C−H borylation with pinBH catalyzed by
cooperating Fe and Cu: Mazzacano, T. J.; Mankad, N. P. J. Am. Chem.
Soc. 2013, 135, 17258−17261.
Typical experimental procedure, tables of selected results,
characterization data of all products, DFT calculation details
1
and geometries, copies of H and 13C NMR spectra. This
material is available free of charge via the Internet at http://
AUTHOR INFORMATION
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(14) See Supporting Information for details.
Corresponding Author
(15) DPEPhos: (oxidi-2,1-phenylene)bis(diphenylphosphine), S-
Phos: 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl.
(16) Thome,
987.
́
I.; Nijs, A.; Bolm, C. Chem. Soc. Rev. 2012, 41, 979−
Notes
The authors declare no competing financial interest.
(17) For the Pd-catalyzed monoborylation of dibromoarenes, see:
(a) Lee, Y.; Kelly, M. J. Tetrahedron Lett. 2006, 47, 4897−4901.
Generally, these compounds were prepared via Br−Li or Br−Mg
exchange: (b) Onoe, M.; Baba, K.; Kim, Y.; Kita, Y.; Tobisu, M.;
Chatani, N. J. Am. Chem. Soc. 2012, 134, 19477−19488. (c) Tobisu,
M.; Chatani, N. J. Am. Chem. Soc. 2012, 134, 19477−19488.
(d) Nagaki, A.; Moriwaki, Y.; Yoshida, J. Chem. Commun. 2012, 48,
11211. (e) Laza, C.; Pintaric, C.; Olivero, S.; Dunach, E. Electrochim.
Acta 2005, 50, 4897−4901 and ref 3a; see also ref 9 for
monoborylation of a diiodide.
(18) See ref 9 for PDB in borylation with B2pin2.
(19) Lam, K. C.; Marder, T. B.; Lin, Z. Organometallics 2010, 29,
1849−1857.
(20) (a) Suseela, Y.; Periasamy, M. J. Organomet. Chem. 1993, 450,
47−52. (b) PraveenGanesh, N.; D’Hondt, S.; Chavant, P. Y. J. Org.
Chem. 2007, 72, 4510−4514.
(21) Involvement of borohydrides is possible: Narisada, M.; Horibe,
I.; Watanabe, F.; Takeda, K. J. Org. Chem. 1989, 54, 5308−5313. 1B
NMR indicated traces of disproportionation of pinBH in the reaction
conditions; see: Westcott, S. A.; Blom, H. P.; Marder, T. B.; Baker, R.
T.; Calabrese, J. C. Inorg. Chem. 1993, 32, 2175−2182.
(22) Nanoparticles of FeB alloys from FeIII and boranes: He, T.;
Wang, J.; Wu, G.; Kim, H.; Proffen, T.; Wu, A.; Li, W.; Liu, T.; Xiong,
Z.; Wu, C.; Chu, H.; Guo, J.; Autrey, T.; Zhang, T.; Chen, P. Chem.
Eur. J. 2010, 16, 12814−12817.
(23) (a) Kays, D. L.; Aldridge, S. Struct. Bonding (Berlin) 2008, 130,
29−122. (b) Hartwig, J. F. Acc. Chem. Res. 2012, 45, 864−873.
(c) Dang, L.; Lin, Z.; Marder, T. B. Chem. Commun. 2009, 3987.
(24) Fomina, L.; Vazquez, B.; Tkatchouk, E.; Fomine, S. Tetrahedron
2002, 58, 6741−6747. 1,2-Diaminoethane was used to model
TMEDA.
ACKNOWLEDGMENTS
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This research was supported by the French Agence Nationale
de la Recherche, program EMMA 043-01, 2011-14 (BORO-
CAT).
REFERENCES
■
(1) (a) Hall, D. G. Boronic acids: preparation and applications in
organic synthesis and medicine; Wiley-VCH Verlag GmbH: Weinheim,
2005. (b) Roughley, S. D.; Jordan, A. M. J. Med. Chem. 2011, 54,
3451−3479.
(2) More than 2000 patents and 1000 articles describe Suzuki
coupling reactions with cyclic boronic esters. For instance:
(a) Myslinska, M.; Heise, G. L.; Walsh, D. J. Tetrahedron Lett. 2012,
53, 2937−2941. (b) Bethel, P. A.; Campbell, A. D.; Goldberg, F. W.;
Kemmitt, P. D.; Lamont, G. M.; Suleman, A. Tetrahedron 2012, 68,
5434−5444. (c) Asano, S.; Kamioka, S.; Isobe, Y. Tetrahedron 2012,
68, 272−279. See also refs 3, 4, and 6.
(3) (a) Demory, E.; Blandin, V.; Einhorn, J.; Chavant, P. Y. Org.
Process Res. Dev. 2011, 15, 710−716. (b) Leermann, T.; Leroux, F. R.;
Colobert, F. Org. Lett. 2011, 13, 4479−4481. (c) Billingsley, K. L.;
Buchwald, S. L. Angew. Chem., Int. Ed. 2008, 47, 4695−4698.
(4) (a) Ishiyama, T.; Murata, M.; Miyaura, N. J. Org. Chem. 1995, 60,
7508−7510. (b) Murata, M.; Watanabe, S.; Masuda, Y. J. Org. Chem.
1997, 62, 6458−6459.
(5) Note that B2pin2 is now available in bulk for <$1/g.
(6) Reviews: (a) Chow, W. K.; Yuen, O. Y.; Choy, P. Y.; So, C. M.;
Lau, C. P.; Wong, W. T.; Kwong, F. Y. RSC Adv. 2013, 3, 12518−
12539. (b) Murata, M. Heterocycles 2012, 85, 1795−1819.
Pd
(25) (a) Lin, Z. Struct. Bonding (Berlin) 2008, 130, 123−148.
(b) Lillo, V.; Fructos, M. R.; Ramírez, J.; Braga, A. A. C.; Maseras, F.;
catalysis: (c) PraveenGanesh, N.; Demory, E.; Gamon, C.; Blandin, V.;
Chavant, P. Y. Synlett 2010, 2403−2406. Ni catalysis: (d) Murata, M.;
Sogabe, Y.; Namikoshi, T.; Watanabe, S. Heterocycles 2012, 86, 133.
(e) Zhang, N.; Hoffman, D. J.; Gutsche, N.; Gupta, J.; Percec, V. J.
Org. Chem. 2012, 77, 5956−5964. (f) Leowanawat, P.; Zhang, N.;
Percec, V. J. Org. Chem. 2012, 77, 1018−1025.
Díaz-Requejo, M. M.; Per
́
ez, P. J.; Fernan
́
dez, E. Chem.Eur. J. 2007,
13, 2614−2621. (c) Pandey, K. K. Dalton Trans. 2012, 41, 3278−3286.
(d) Alcaraz, G.; Sabo-Etienne, S. Angew. Chem., Int. Ed. 2010, 49,
7170−7179. (e) Schlecht, S.; Hartwig, J. F. J. Am. Chem. Soc. 2000,
122, 9435−9443.
(7) C−H borylation of arenes or alkanes: (a) Szabo, K. J. C−B and
C−Si bond-forming reactions by C−H functionalization. In Science of
Synthesis: Cross Coupling and Heck-Type Reactions; Molander, G., Ed.;
Thieme: New York, 2013; Vol. 2; p 485. (b) Hartwig, J. F. Acc. Chem.
Res. 2012, 45, 864−873. (c) Mkhalid, I. A. I.; Barnard, J. H.; Marder,
T. B.; Murphy, J. M.; Hartwig, J. F. Chem. Rev. 2010, 110, 890−931.
(8) Zhu, W.; Ma, D. Org. Lett. 2006, 8, 261−263.
(26) Approaches of NaH led to coordination of the hydride to Cu,
and we did not find a transition state for a subsequent evolution of H2.
(27) (a) Yang, C.-T.; Zhang, Z.-Q.; Tajuddin, H.; Wu, C.-C.; Liang,
J.; Liu, J.-H.; Fu, Y.; Czyzewska, M.; Steel, P. G.; Marder, T. B.; Liu, L.
Angew. Chem., Int. Ed. 2012, 51, 528−532. (b) Ito, H.; Kubota, K. Org.
Lett. 2012, 14, 890−893.
(9) Kleeberg, C.; Dang, L.; Lin, Z.; Marder, T. B. Angew. Chem., Int.
Ed. 2009, 48, 5350−5354.
(10) (a) Per
́
ez-Temprano, M. H.; Casares, J. A.; Espinet, P. Chem.
Eur. J. 2012, 18, 1864−1884. (b) Lee, J. M.; Na, Y.; Han, H.; Chang, S.
Chem. Soc. Rev. 2004, 33, 302.
(11) (a) Hedstrom, A.; Lindstedt, E.; Norrby, P.-O. J. Organomet.
̈
̀
Chem. 2013, 748, 51−55. (b) Lefevre, G.; Taillefer, M.; Adamo, C.;
Ciofini, I.; Jutand, A. Eur. J. Org. Chem. 2011, 2011, 3768−3780. (c)
Organoiron compounds in PATAI’S Chemistry of Functional Groups;
2369
dx.doi.org/10.1021/ol500675q | Org. Lett. 2014, 16, 2366−2369