ACS Catalysis
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Notes
The authors declare no competing financial interest.
Scheme 3. Disubstituted alkene
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ACKNOWLEDGMENT
Financial support was provided by the National 973 Pro-
gram (2015CB856600) and NSFC (21472162).
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REFERENCES
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Scheme 4. Deuterium experiments and plausible mechan-
ism.
1
For a review on catalytic selective synthesis, see: (a) Mahatthananchai,
J.; Dumas, A. M.; Bode, J. W. Angew. Chem., Int. Ed. 2012, 51, 10954-
10990. For selected catalytic regioselectivity-controllable hydroboration
or elementboration reactions, see: [Pd] (b) Ohmura, T.; Oshima, K.; Ta-
niguchi, H.; Suginome, M. J. Am. Chem. Soc. 2010, 132, 12194-12196;
(c) Deng, Y.; Bartholomeyzik, T.; Bäckvall, J.-E. Angew. Chem., Int.
Ed. 2013, 52, 6283-6287; (d) Ojha, D. P.; Prabhu, K. R. Org. Lett. 2016,
18, 432-435; [Cu] (e) Jang, H.; Zhugralin, A. R.; Lee, Y.; Hoveyda, A.
H. J. Am. Chem. Soc. 2011, 133, 7859-7871; (f) Park, J. K.; Ondrusek,
B. A.; McQuade, D. T. Org. Lett. 2012, 14, 4790-4793; (g) Sakae, R.;
Hirano, K.; Miura, M. J. Am. Chem. Soc. 2015, 137, 6460-6463; (h) Su,
W.; Gong, T.-J.; Lu, X.; Xu, M.-Y.; Yu, C.-G.; Xu, Z.-Y.; Yu, H.-Z.;
Xiao, B.; Fu, Y. Angew. Chem., Int. Ed. 2015, 54, 12957-12961; (i)
Iwamoto, H.; Kubota, K.; Ito, H. Chem. Coummun. 2016, 52, 5916-
5919. (j) Jang, W. J.; Lee, W. L.; Moon, J. H.; Lee, J. Y.; Yun, J. Org.
Lett. 2016, 18, 1390-1393; (k) Xi, Y.; Hartwig, J. F. J. Am. Chem. Soc.
2016, 138, 6703-6706.
2
For selected reviews, see: (a) Burgess, K.; Ohlmeyer, M. J. Chem. Rev.
1991, 91. 1179-1191; (b) Greenhalgh, M. D.; Jones, A. S.; Thomas, S. P.
ChemCatChem 2015, 7, 190-222; (c) Yoshida, H. ACS Catal. 2016, 6,
1799-1811; For selected examples on catalytic hydroboration of alkenes
and alkynes, see: (d) Wu, J. Y.; Moreau, B.; Ritter, T. J. Am. Chem. Soc.
2009, 131, 12915-12917; (e) Ohmura, T.; Yamamoto, Y.; Miyaura, N. J.
Am. Chem. Soc. 2000, 122, 4990-4991; (f) Gunanathan, C.; Hölscher,
M.; Pan, F.; Leitner, W. J. Am. Chem. Soc. 2012, 134, 14349-14352; (g)
Haberberger, M.; Enthaler, S.; Chem. Asian J. 2013, 8, 50-54; (h) Obli-
gacion, J. V.; Chirik, P. J. Org. Lett. 2013, 15, 2680-2683; (i) Zhang, L.;
Peng, D.; Leng, X.; Huang, Z. Angew. Chem., Int. Ed. 2013, 52, 3676-
3680. (j) Greenhalgh, M. D.; Thomas, S. P.; Chem. Commun. 2013, 49,
11230-11232; (k) Tseng, K.-N. T.; Kampf, J. W.; Szymczak, N. K. ACS
Catal. 2015, 5, 411-415.
In summary, we have developed a ligand-controlled cobalt-
catalyzed regioselective hydroboration/cyclization of 1,6-
enynes to afford alkenylboronates and alkylboronates, respec-
tively. The reactions could be easily scaled up and the boro-
nate products could be derivatized to various useful com-
pounds. A primary mechanism was proposed based on sub-
strate-controlled experiments and deuterium experiments. This
interesting side-arm-effect phenomenon will encourage us to
explore more examples and mechanistic details on selectivity-
controllable reactions by using multi-dentate ligands with non-
precious transition metals.
3 (a) In Organic Synthesis via Organoboranes; Brown, H. C., Ed.; Wiley-
Interscience: New York, 1975. (b) In Organoboron Compounds in Or-
ganic Synthesis; Mikhailov, B. M.; Bubnov, Y. N. Eds.; Harwood Aca-
demic Publishers, 1984. (c) In Contemporary Boron Chemistry; David-
son, M. G., Wade, K., Marder, T. B., Hughes, A. K. Eds.; Royal Society
of Chemistry: Cambridge, UK, 2000. (d) In Organoboranes for Syn-
theses, ACS Symposium Series 783; Ramachandran, P. V., Brown, H.
C., Eds.; American Chemical Society: Washington, DC, 2001. (e) In
Boronic Acids: Preparation and Applications in Organic Synthesis,
Medicine and Materials (Volume 1 and 2), 2nd ed.; Hall, D. G., Ed.;
Wiley-VCH: Weinheim, Germany, 2011. (f) Hartwig, J. F. Acc. Chem.
Res. 2012, 45, 864-873.
ASSOCIATED CONTENT
Supporting Information.
4 For selected reviews on transition-metal-catalyzed cyclization of 1,6-
enynes, see: (a) Trost, B. M. Acc. Chem. Res. 1990, 23, 34-42. (b) Au-
bert, C.; Buisine, O.; Malacria, M. Chem. Rev. 2002, 102, 813-834. (c)
Marinetti, A.; Jullien, H.; Voituriez, A. Chem. Soc. Rev. 2012, 41,
4884-4908.
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acscatal..
Procedures and analytical data (PDF)
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Kinder, R. E.; Widenhoefer, R. A. Org. Lett. 2006, 8, 1967-1969.
Liu, P.; Fukui, Y.; Tian, P.; He, Z.-T.; Sun, C.-Y.; Wu, N.-Y.; Lin, G.-Q.
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J. Am. Chem. Soc. 2013, 135, 11700-11703.
7 For selected examples on substrate-controlled regioselective borylative
cyclization of 1,6-enynes with (BPin)2, see: (a) Marco-Martínez, J.;
López-Carrillo, V.; Buñuel, E.; Simancas, R.; Cárdenas, D. J. J. Am.
Chem. Soc. 2007, 129, 1874-1875. (b) Marco-Martínez, J.; Buñuel, E.;
Muñoz-Rodríguez, R.; Cárdenas, D. J. Org. Lett. 2008, 10, 3619-3621;
(c) Pardo-Rodríguez, V.; Marco-Martínez, J.; Buñuel, E.; Cárdenas, D.
X-ray diffraction of compound 3m (cif)
AUTHOR INFORMATION
Corresponding Author
*E-mail: luzhan@zju.edu.cn
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