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Or gP al en ai sc e& d Bo i on mo to al ed cj uu ls at r mC ha re gmi ni ss try
DOI: 10.1039/C8OB01974F
Journal Name
COMMUNICATION
diaminobenzenes in high yields with excellent chemo- and
regioselectivities. Bulky alkyl groups attached on the amino
group plays a pivotal role in prevention of side-reactions such
as dealkylation without compromising reactivity at the
sterically congested ortho position. The ortho selectivity
observed is rationalized in terms of the coordination of the
dialkylamino group to the Lewis acidic nitrogen atom of the
Rh(II)-nitrene intermediate. This method represents the first
example of regiocontrol in Rh(II)-catalyzed C−H aminaꢀon by
harnessing non-covalent interaction between substrates and
Rh(II)-nitrene intermediates. Further studies on the extension
of substrate scope as well as theoretical studies are currently
8
Very recentry, Kawabata, Ueda and co-workers reported a
Rh(II)-catalyzed para C−H aminaꢀon of phenyl ethers using
TrocNHOTs as a nitrene precursor; K. Arai, Y. Ueda, K.
Morisaki, T. Furuta, T. Sasamori, N. Tokitoh and T. Kawabata,
Chem. Commun., 2018, 54, 2264.
9
1
In 2004, Che and co-workers reported that the reaction of
furan with TsN=IPh provided C(sp )−H amination product in
2
2
1% under the catalysis of Rh
2
(OAc)
4
. L. He, P. W. H. Chan,
, 2405.
W.-M. Tsui, W.-Y. Yu and C.-M. Che, Org. Lett., 2004,2
6
0 For examples of Rh(II)-catalyzed intramolecular C(sp )−H
amination, see: (a) S. Chiba, G. Hattori and K. Narasaka,
Chem. Lett., 2007, 36, 52; (b) B. J. Stokes, B. Jovanović, H.
Dong, K. J. Richert, R. D. Riell and T. G. Driver, J. Org. Chem.,
2
ACS Catal., 2016, , 6520.
009, 74, 3225; (c) R. Singh, K. Nagesh and M. Parameshwar,
6
3
0
in progress.
2
1
1 For intermorecular C(sp )−H aminaꢀon with metal-nitrenes
derived from Cu, Au and Fe catalysts, see: (a) M. M. Díaz-
Requejo, T. R. Belderraín, M. C. Nicasio, S. Trofimenko, and P.
J. Pérez, J. Am. Chem. Soc., 2003, 125, 12078; (b) C. W.
Hamilton, D. S. Laitar and J. P. Sadighi, Chem. Commun., 2004,
Acknowledgements
This work is financially supported by a Grant-in-Aid for Young
Scientists (B) (No. 17K15428) from JSPS, Japan. We thank T.
Koseki of the Analytical Center of Meiji Pharmaceutical
University for mass spectral measurements.
1
628; (c) M. R. Fructos, S. Trofimenko, M. Mar Díaz-Requejo
and P. J. Pérez, J. Am. Chem. Soc., 2006, 128, 11784; (d) Z. Li,
D. A. Capretto, R. O. Rahaman and C. He, J. Am. Chem. Soc.,
2
007, 129, 12058; (e) S. Liang and M. P. Jensen,
Organometallics, 2012, 31, 8055; (f) A. John, J. Byun and K.
M. Nicholas, Chem. Commun., 2013, 49, 10965.
2 M. Ito, A. Tanaka, K. Higuchi and S. Sugiyama, Eur. J. Org.
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3 V. Bagchi, P. Paraskevopoulou, P. Das, L. Chi, Q. Wang. A.
Choudhury, J. S. Mathieson, L. Cronin, D. B. Pardue, T. R.
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1
1
Notes and references
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4 For examples of Rh(II)- and Ag-catalyzed N−N bond
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1
1
5 Bulky dialkylamino group plays a pivotal role in prevention of
Ortho C−H azidaꢀon and nitraꢀon of anilines are also
effective for the synthesis of precursor of 1,2-
diaminobenzenes. (a) C. Tang and N. Jiao, J. Am. Chem. Soc.,
over-oxidation of ortho amination products
9 and Scheme S1 in ESI.
6 We previously reported that Rh
superior performance to Rh (esp)
2. See reference
1
2
(HNCOCF
3 4
) displayed
in reactions with sterically
2012, 134, 18924; (b) G. G. Pawar, A. Brahmanandan and M.
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While the formation of metallacycles from N,N-
dialkylbenzylamines is well-known, there is no report of the
formation of four membered metallacycles from N,N-
dialkylanilines. (a) G. Cai, Y. Fu, Y. Li, X. Wan and Z. Shi, J. Am.
Chem. Soc., 2007, 129, 7666; (b) A. McNally, B. Haffemayer,
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2
2
congested ortho-substituted anilines. See reference 12.
7 No reaction was observed with N-isopropylacetanilide
probably due to the low nucleophilicity of the substrate.
8 Ortho-substituted anilines were not examined because of
difficulty in preparation of the substrates.
9 CCDC 1828111 contains the supplementary crystallographic
data for this paper.
0 Competition experiments between 1d and 7 or 1d and 2v
under the C−H aminaꢀon condiꢀons indicated that a bulky
dialkylamino group plays a crucial role in prevention of over-
oxidation of 2 as well as dealkylation of substrates 1 (see
Table 1, entries 1−4). See Scheme S1 in ESI for details.
1 T. Kawakami, K. Murakami and K. Itami, J. Am. Chem. Soc.,
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1
1
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(
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4 Recently, Musaev and Berry reported that Rh-nitrene species
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is heavily polarized toward the nitrogen atom. A. Varela-
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