Journal of the American Chemical Society
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Carbene-Catalyzed β-Hydroxylation of Enals Using Nitroarenes: An Atom
ASSOCIATED CONTENT
Transfer Reaction That Proceeds via Single Electron Transfer. J. Am. Chem.
Soc. 2014, 136, 14674. (g) White, N. A.; Rovis, T. Oxidatively Initiated
NHC-Catalyzed Enantioselective Synthesis of 3,4-Disubstituted
Cyclopentanones from Enals. J. Am. Chem. Soc. 2015, 137, 10112. (h)
Rehbein, J.; Ruser, S. M.; Phan, J. NHC-catalysed benzoin condensation –
is it all down to the Breslow intermediate? Chem. Sci. 2015, 6, 6013. (i)
Yang, W.; Hu, W.; Dong, X.; Li, X.; Sun, J. N-Heterocyclic Carbene
Catalyzed γ-Dihalomethylenation of Enals by Single-Electron Transfer.
Angew. Chem., Int. Ed. 2016, 55, 15783. (j) Chen, X.−Y.; Chen, K.−Q.;
Sun, D.−Q.; Ye, S. N-Heterocyclic carbene-catalyzed oxidative [3 + 2]
annulation of dioxindoles and enals: cross coupling of homoenolate and
enolate. Chem. Sci. 2017, 8, 1936. (k) Zhao, K.; Enders, D. Merging
N‐Heterocyclic Carbene Catalysis and Single Electron Transfer: A New
Strategy for Asymmetric Transformations. Angew. Chem., Int. Ed., 2017,
56, 3754.
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Supporting Information. Experimental details and
characterization data for all new compounds (PDF). This
material is available free of charge via the Internet at
AUTHOR INFORMATION
Corresponding Authors
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Kazunori Nagao: nkazunori@p.kanazawa-u.ac.jp
Hirohisa Ohmiya: ohmiya@p.kanazawa-u.ac.jp
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(6) (a) Nakanishi, I.; Itoh, S.; Suenobu, T.; Inoue, H.; Fukuzumi, S.; Chem. Lett.
Redox Behavior of Active Aldehydes Derived from Thiamin Coenzyme
Analogs. Chem. Lett. 1997, 8, 707. (b) Nakanishi, I.; Itoh, S.; Suenobu, T.;
Fukuzumi, S. Electron transfer properties of active aldehydes derived from
thiamin coenzyme analogues. Chem. Commun., 1997, 1927. (c) Nakanishi,
I.; Itoh, S.; Fukuzumi, S. Electron-Transfer Properties of Active Aldehydes
of Thiamin Coenzyme Models, and Mechanism of Formation of the
Reactive Intermediates. Chem. Eur. J. 1999, 5, 2810. (d) Nakanishi, I.; Itoh,
S.; Suenobu, T.; Fukuzumi, S. Direct Observation of Radical Intermediates
While Investiganting the Redox Behavior of Thiamin Coenzyme Models.
Angew. Chem., Int. Ed., 1998, 37, 2992.
(7) For our synergistic NHC-based catalysis, see: (a) Yasuda, S.; Ishii, T.;
Takemoto, S.; Haruki, H.; Ohmiya, H. Synergistic N-Heterocyclic
Carbene/Palladium-Catalyzed Reactions of Aldehyde Acyl Anions with
either Diarylmethyl or Allylic Carbonates. Angew. Chem. Int. Ed. 2018, 57,
2938. (b) Haruki, H.; Yasuda, S.; Nagao, K.; Ohmiya, H. Dehydrative
Allylation between Aldehydes and Allylic Alcohols through Synergistic N-
Heterocyclic Carbene/Palladium Catalysis. Chem. Eur. J. 2019, 25, 724.
(c) Takemoto, S.; Ishii, T.; Yasuda, S.; Ohmiya, H. Synergistic N-
Heterocyclic Carbene/Palladium-Catalyzed Allylation of Aldehydes with
Allylic Carbonates. Bull. Chem. Soc. Jpn. 2019, 48, DOI:
10.1246/bcsj.20190012.
(8) For selected papers on synthesis of ketones via formyl C–H activation of
aldehydes, see: (a) Huang, Y.-C.; Majumdar, K. K.; Cheng, C.-H. Nickel-
Catalyzed Coupling of Aryl Iodides with Aromatic Aldehydes:ꢀ
Chemoselective Synthesis of Ketones. J. Org. Chem. 2002, 67, 1682. (b)
Pucheault, M.; Darses, S.; Genet, J.-P. Direct Access to Ketones from
Aldehydes via Rhodium-Catalyzed Cross-Coupling Reaction with
Potassium Trifluoro(organo)borates. J. Am. Chem. Soc. 2004, 126, 15356.
(c) Ko, S.; Kang, B.; Chang, S. Cooperative catalysis by Ru and Pd for the
direct coupling of a chelating aldehyde with iodoarenes or organostannanes.
Angew. Chem., Int. Ed. 2005, 44, 455. (d) Ruan, J.; Saidi, O.; Iggo, J. A.;
Xiao, J. Direct Acylation of Aryl Bromides with Aldehydes by Palladium
Catalysis. J. Am. Chem. Soc. 2008, 130, 10510. (e) Suchand, B.;
Satyanarayana, G. Palladium-Catalyzed Environmentally Benign
Acylation. J. Org. Chem. 2016, 81, 6409. (f) Zhang, X.; MacMillan, D. W.
C. Direct Aldehyde C–H Arylation and Alkylation via the Combination of
Nickel, Hydrogen Atom Transfer, and Photoredox Catalysis. J. Am. Chem.
Soc. 2017, 139, 11353. (g) Mukherjee, S.; Garza-Sanchez, R. A.; Tlahuext-
Aca, A.; Glorius, F. Alkynylation of Csp2 (O)-H Bonds Enabled by
Photoredox-Mediated Hydrogen-Atom Transfer. Angew. Chem., Int. Ed.
2017, 56, 14723.
ORCID
Kazunori Nagao: 0000-0003-3141-5279
Hirohisa Ohmiya: 0000-0002-1374-1137
ACKNOWLEDGMENT
This work was supported by JSPS KAKENHI Grant Number
JP18H01971 to Scientific Research (B), JSPS KAKENHI Grant
Number JP17H06449 (Hybrid Catalysis), Kanazawa University
SAKIGAKE project 2018.
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