Organic Letters
Letter
19107−19110. (e) Tseng, K.-N. T.; Kampf, J. W.; Szymczak, N. K.
Regulation of Iron-Catalyzed Olefin Hydroboration by Ligand
Modifications at a Remote Site. ACS Catal. 2015, 5, 411−415.
(f) Greenhalgh, M. D.; Thomas, S. P. Chemo-, regio-, and
stereoselective iron-catalysed hydroboration of alkenes and alkynes.
Chem. Commun. 2013, 49, 11230−11232.
(6) (a) Nakajima, K.; Kato, T.; Nishibayashi, Y. Hydroboration of
Alkynes Catalyzed by Pyrrolide-Based PNP Pincer−Iron Complexes.
Org. Lett. 2017, 19, 4323−4326. (b) Ben-Daat, H.; Rock, C. L.;
Flores, M.; Groy, T. L.; Bowman, A. C.; Trovitch, R. J. Hydroboration
of alkynes and nitriles using an α-diimine cobalt hydride catalyst.
Chem. Commun. 2017, 53, 7333−7336.
(10) (a) Noh, D.; Chea, H.; Ju, J.; Yun, J. Highly regio- and
enantioselective copper-catalyzed hydroboration of styrenes. Angew.
Chem., Int. Ed. 2009, 48, 6062−6064. (b) Iwamoto, H.; Kubota, K.;
Ito, H. Highly selective Markovnikov hydroboration of alkyl-
substituted terminal alkenes with a phosphine−copper(I) catalyst.
Chem. Commun. 2016, 52, 5916−5919. (c) Romero, E. A.; Jazzar, R.;
Bertrand, G. (CAAC)CuX-catalyzed hydroboration of terminal
alkynes with pinacolborane directed by the X-ligand. J. Organomet.
Chem. 2017, 829, 11−13. (d) Wyss, C.; Bitting, J.; Bacsa, J.; Gray, T.
G.; Sadighi, J. P. Bonding and Reactivity of a Dicopper(I) μ−Boryl
Cation. Organometallics 2016, 35, 71−74. (e) Zeng, X.; Gong, C.;
Guo, H.; Xu, H.; Zhang, J.; Xie, J. Efficient Heterogeneous
Hydroboration of Alkynes: Enhancing the Catalytic Activity by
Cu(0) Incorporated CuFe2O4 nanoparticles. New J. Chem. 2018, 42,
17346−17350. (f) Zhang, Q.; Liu, Y.; Wang, T.; Zhang, X.; Long, C.;
Wu, Y.-D.; Wang, M.-X. Mechanistic Study on Cu(II)-Catalyzed
Oxidative Cross-Coupling Reaction between Arenes and Boronic
Acids under Aerobic Conditions. J. Am. Chem. Soc. 2018, 140, 5579−
5587.
(11) To the best of our knowledge, only one example on the
hydrosilylation of ketones was reported using copper(II) acetate
complexes of biphosphine ligands. See: Zhou, J.-N.; Fang, Q.; Hu, Y.-
H.; Yang, L.-Y.; Wu, F.-F.; Xie, L.-J.; Wu, J.; Li, S. Copper(II)-
catalyzed enantioselective hydrosilylation of halo-substituted alkyl aryl
and heteroaryl ketones: asymmetric synthesis of (R)-fluoxetine and
(S)-duloxetine. Org. Biomol. Chem. 2014, 12, 1009−1017.
(12) Bagherzadeh, S.; Mankad, N. P. Extremely efficient hydro-
boration of ketones and aldehydes by copper carbene catalysis. Chem.
Commun. 2016, 52, 3844−3846.
(13) Docherty, J. H.; Peng, J.; Dominey, A. P.; Thomas, S. P.
Activation and discovery of earth-abundant metal catalysts using
sodium tert-butoxide. Nat. Chem. 2017, 9, 595−600.
(7) Das, U. K.; Higman, C. S.; Gabidullin, B.; Hein, J. E.; Baker, R.
T. Efficient and Selective Iron-Complex-Catalyzed Hydroboration of
Aldehydes. ACS Catal. 2018, 8, 1076−1081 and references cited
therein .
(8) For a recent review, see: (a) Chong, C. C.; Kinjo, R. Catalytic
Hydroboration of Carbonyl Derivatives, Imines, and Carbon Dioxide.
ACS Catal. 2015, 5, 3238−3259. For selected examples, see:
(b) Lummis, P. A.; Momeni, M. R.; Lui, M. W.; McDonald, R.;
Ferguson, M. J.; Miskolzie, M.; Brown, A.; Rivard, E. Accessing zinc
monohydride cations through coordinative interactions. Angew.
Chem., Int. Ed. 2014, 53, 9347−9351. (c) Arrowsmith, M.;
Hadlington, T. J.; Hill, M. S.; Kociok-Kohn, G. Magnesium-catalysed
hydroboration of aldehydes and ketones. Chem. Commun. 2012, 48,
4567−4569. (d) Mukherjee, D.; Ellern, A.; Sadow, A. D. Magnesium-
catalyzed hydroboration of esters: evidence for a new zwitterionic
mechanism. Chem. Sci. 2014, 5, 959−964. (e) Guo, J.; Chen, J.; Lu, Z.
Cobalt-catalyzed asymmetric hydroboration of aryl ketones with
pinacolborane. Chem. Commun. 2015, 51, 5725−5727. (f) Oluyadi, A.
A.; Ma, S.; Muhoro, C. N. Titanocene(II)-Catalyzed Hydroboration
of Carbonyl Compounds. Organometallics 2013, 32, 70−78. (g) Yang,
Z.; Zhong, M.; Ma, X.; De, S.; Anusha, C.; Parameswaran, P.; Roesky,
H. W. An Aluminum Hydride That Functions like a Transition-Metal
Catalyst. Angew. Chem., Int. Ed. 2015, 54, 10225−10229. (h) Jakhar,
V. K.; Barman, M. K.; Nembenna, S. Aluminum Monohydride
Catalyzed Selective Hydroboration of Carbonyl Compounds. Org.
Lett. 2016, 18, 4710−4713. (i) Wang, W.; Shen, X.; Zhao, F.; Jiang,
H.; Yao, W.; Pullarkat, S. A.; Xu, L.; Ma, M. Ytterbium-Catalyzed
Hydroboration of Aldehydes and Ketones. J. Org. Chem. 2018, 83,
69−74. (j) Tamang, S. R.; Findlater, M. Iron Catalyzed Hydro-
boration of Aldehydes and Ketones. J. Org. Chem. 2017, 82, 12857−
12860. (k) Baishya, A.; Baruah, S.; Geetharani, K. Efficient
Hydroboration of Carbonyls by an Iron(II) Amide Catalyst. Dalton
Trans. 2018, 47, 9231−9236. (l) Kaithal, A.; Chatterjee, B.;
Gunanathan, C. Ruthenium Catalyzed Selective Hydroboration of
Carbonyl Compounds. Org. Lett. 2015, 17, 4790−4793.
(14) Zhang, G.; Proni, G.; Zhao, S.; Constable, E. C.; Housecroft, C.
E.; Zampese, J. A.; Neuburger, M. Chiral tetranuclear and dinuclear
copper(II) complexes for TEMPO-mediated aerobic oxidation of
alcohols: are four metal centres better than two? Dalton Trans. 2014,
43, 12313−12320.
(15) Cho, W. K.; Lee, J. K.; Kang, S. M.; Chi, Y. S.; Lee, H.-S.; Choi,
I. S. Gold-Catalyzed Cyanosilylation Reaction: Homogeneous and
Heterogeneous Pathways. Chem. - Eur. J. 2007, 13, 6351−6358.
(9) (a) Wu, J.; Zeng, H.; Cheng, J.; Zheng, S.; Golen, J. A.; Manke,
D. R.; Zhang, G. Cobalt(II) Coordination Polymer as a Precatalyst for
Selective Hydroboration of Aldehydes, Ketones, and Imines. J. Org.
Chem. 2018, 83, 9442−9448. (b) Li, L.; Liu, E.; Cheng, J.; Zhang, G.
Iron(II) coordination polymer catalysed hydroboration of ketones.
Dalton. Trans. 2018, 47, 9579−9584. (c) Eedugurala, N.; Wang, Z.;
Chaudhary, U.; Nelson, N.; Kandel, K.; Kobayashi, T.; Slowing, I. I.;
Pruski, M.; Sadow, A. D. Mesoporous Silica-Supported Amidozirco-
nium-Catalyzed Carbonyl Hydroboration. ACS Catal. 2015, 5, 7399−
7414. (d) Manna, K.; Ji, P.; Greene, F. X.; Lin, W. Metal−Organic
Framework Nodes Support Single-Site Magnesium−Alkyl Catalysts
for Hydroboration and Hydroamination Reactions. J. Am. Chem. Soc.
2016, 138, 7488−7491. (e) Huang, Z.; Liu, D.; Camacho-Bunquin, J.;
́
́
Zhang, G.; Yang, D.; Lopez-Encarnacion, J. M.; Xu, Y.; Ferrandon, J.
K.; Poluektov, O. G.; Jellinek, J.; Lei, A.; Bunel, E. E.; Delferro, M.
Supported Single-Site Ti(IV) on a Metal−Organic Framework for the
Hydroboration of Carbonyl Compounds. Organometallics 2017, 36,
3921−3930. (f) Manna, K.; Ji, P.; Lin, Z.; Greene, F. X.; Urban, A.;
Thacker, N. C.; Lin, W. Chemoselective Single-Site Earth-Abundant
Metal Catalysts at Metal-Organic Framework Nodes. Nat. Commun.
2016, 7, 12610−12621.
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