Journal of the American Chemical Society
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4023. For selected applications of amine- and phosphine-boron adducts
from safe and readily accessible ene-yne-carbonyl carbene pre-
cursors and borane adducts under mild reaction conditions. The
B–H bond insertion products could be easily converted to
widely used pinacolborates, MIDA borates, and diaryl metha-
nol compounds. Kinetics experiments showed that the reaction
is first order with respect to the concentrations of the Cu catalyst
and the alkyne substrate and zero order with respect to the con-
centrations of the borane adduct. Both the kinetics experiments
and density functional theory calculations suggest that for-
mation of a metal carbene is involved in the rate-limiting step
and that B–H bond insertion is a fast, concerted process. This
successful use of alkynes as carbene precursors in B–H bond
insertion reactions opens up a new route to organoboron com-
pounds.
1
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ASSOCIATED CONTENT
Supporting Information.
Metrical parameters for the structure (S)-(+)-3ac are available free
of charge from the Cambridge Crystallographic Data Centre under
reference numbers CCDC-1531867. Experimental procedures and
spectral data. The Supporting Information is available free of
̈
(10) For selected reviews, see: (a) Furstner, A.; Davies, P. W. Angew.
Chem., Int. Ed. 2007, 46, 3410. (b) Jiménez-Núñez, E.; Echavarren, A.
M. Chem. Rev. 2008, 108, 3326. (c) Zhang, L. Acc. Chem. Res. 2014,
47, 877. (d) Yeom, H.-S.; Shin, S. Acc. Chem. Res. 2014, 47, 966. (e)
Qian, D.; Zhang, J. Chem. Soc. Rev. 2015, 44, 677. (f) Jia, M.; Ma, S.
Angew. Chem., Int. Ed. 2016, 55, 9134.
AUTHOR INFORMATION
Corresponding Author
(11) For reviews on ene-yne-carbonyls as a carbene source, see: (a)
Miki, K.; Uemura, S.; Ohe, K. Chem. Lett. 2005, 34, 1068. (b) Kusama,
H.; Iwasawa, N. Chem. Lett. 2006, 35, 1082. (c) Murai, M.; Miki, K.;
Ohe, K. J. Synth. Org. Chem. Jpn. 2009, 67, 1161. For selected trans-
formations of ene-yne-carbonyls via metal carbene intermediates, see:
(d) Miki, K.; Nishino, F.; Ohe, K.; Uemura, S. J. Am. Chem. Soc. 2002,
124, 5260. (e) Barluenga, J.; Riesgo, L.; Vicente, R.; López, L. A.;
Tomás, M. J. Am. Chem. Soc. 2008, 130, 13528. (f) Vicente, R.; Gon-
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López, A.; Vicente, R. Angew. Chem., Int. Ed. 2013, 52, 5853. (h) Xia,
Y.; Qu, S.; Xiao, Q.; Wang, Z.-X.; Qu, P.; Chen, L.; Liu, Z.; Tian, L.;
Huang, Z.; Zhang, Y.; Wang, J. J. Am. Chem. Soc. 2013, 135, 13502.
(i) Zhu, D.; Ma, J.; Luo, K.; Fu, H.; Zhang, L.; Zhu, S. Angew. Chem.,
Int. Ed. 2016, 55, 8452.
(12) For other transformations of ene-yne-imino compounds via
metal carbene intermediates, see: (a) Zhang, Y.; Herndon, J. W. Org.
Lett. 2003, 5, 2043. (b) Nishino, F.; Miki, K.; Kato, Y.; Ohe, K.;
Uemura S. Org. Lett. 2003, 5, 2615. (c) Shen, H.-C.; Li, C.-W.; Liu,
R.-S. Tetrahedron Lett. 2004, 45, 9245.
(13) (a) Aggarwal, V. K.; Binanzer, M.; Ceglie, M. C. D.; Gallanti,
M.; Glasspoole, B. W.; Kendrick, S. J. F.; Sonawane, R. P.; Vázquez-
Romero, A.; Webster, M. P. Org. Lett. 2011, 13, 1490. (b) Guo, J.; Lu,
Z. Angew. Chem., Int. Ed. 2016, 55, 10835.
(14) The chiral dirhodium complexes used in this study are commer-
cial available. For the preparation, see: (a) Davies, H. M. L.; Bruzinski,
P. R.; Lake, D. H.; Kong, N.; Fall, M. J. J. Am. Chem. Soc. 1996, 118,
6897. (b) Qin, C.; Boyarskikh, V.; Hansen, J. H.; Hardcastle, K. I.; Mu-
saev, D. G.; Davies, H. M. L. J. Am. Chem. Soc. 2012, 134, 19198. (c)
Adly, F. G.; Gardiner, M. G.; Ghanem, A. Chem. Eur. J. 2016, 22, 3447.
(15) CCDC 1531867 contains the supplementary crystallographic
data for compound (S)-(+)-3ac. This data can be obtained free of charge
cam.ac.uk/data_request/cif. See SI for details.
(16) For a review on asymmetric carbene insertion into heteroatom-
hydrogen bond, see: Zhu, S.-F.; Zhou, Q.-L. Acc. Chem. Res. 2012, 45,
1365.
(17) (a) He, Z.; Zajdlik, A.; Yudin, A. K. Acc. Chem. Res. 2014, 47,
1029. (b) Li, J.; Grillo, A. S.; Burke, M. D. Acc. Chem. Res. 2015, 48,
2297.
* sfzhu@nankai.edu.cn
* qlzhou@nankai.edu.cn
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
We thank the National Natural Science Foundation of China
(21625204, 21421062, 21532003), the National Basic Research
Program of China (2012CB821600), the “111” project (B06005) of
the Ministry of Education of China, and the National Program for
Support of Top-notch Young Professionals for financial support.
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