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Organic & Biomolecular Chemistry
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ARTICLE
Journal Name
Jo, J. Ju, J. Choe, K. H. Song, S. Lee, J. Org. Chem., 2009, 74
could bind to the acylamidine 1a through a two‐point contact in this
system. The reaction is initiated through intermolecular hydrogen
bonds between hydronium ion and the acylamidine 1a to generate
the intermediate A and subsequently protonate to form the
intermediate B. Then, water attacks the intermediate B, generating
N‐formyl imide 2a and dimethylamine salt. The N‐formyl imide 2a
with TsOH ・ H2O catalyst in water could further convert into
intermediate C by intramolecular hydrogen bonding between 1,3‐
dicarbonyl groups, and react with compounds 3, 5, and 9 to facilitate
N‐formylation to give the desired N‐formamides, benzimidazoles and
quinazolinones, respectively.
6358.
DOI: 10.1039/D0OB01080D
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7
X. Wang, N. Jiang, S. Zhao, S. Xi, J. Wang, T. Jing, W. Zhang,
M. Guo, P. Gong, X. Zhai, Bioorg. Med. Chem., 2017, 25, 886.
(a) R. Obrecht, R. Herrmann, I. Ugi, Synthesis, 1985, 400; (b)
A. Porcheddy, G. Giacomelli, M. Salaris, J. Org. Chem., 2005,
70, 2361; (c) Y. Ichikawa, T. Minami, S. Kusaba, N. Saeki, Y.
Tonegawa, Y. Tomita, K. Nakano, H. Kotsuki, T. Masuda, Org.
Biomol. Chem., 2014, 12, 3924. (d) X. Wang, Q.-G. Wang, Q.-
L. Luo, Synthesis, 2015, 47, 49.
(a) S. Kobayashi, K. Nishio, J. Org. Chem., 1994, 59, 6620; (b)
S. B. Jagtap, S. B. Tsogoeva, Chem. Commun., 2006, 4747.
(a) Z. Wang, S. Wei, C. Wang, J. Sun, Tetrahedron:
Asymmetry, 2007, 18, 705; (b) S. Jones, C. J. A. Warner, Org.
Biomol. Chem., 2012, 10, 2189.
8
9
10 (a) K. A. Stephenson, J. Zubieta, S. R. Banerjee, M. K.
Levadala, L. Taggart, L. Ryan, N. McFarlane, D. R. Boreham,
K. P. Maresca, J. W. Babich, J. F. Valliant, Bioconjugate
Chem., 2004, 15, 128; (b) M. Suchy, A. A. H. Elmehriki, R. H.
E. Hudson, Org. Lett., 2011, 13, 3952.
11 (a) S. H. Jung, J. H. Ahn, S. K. Park, J.-K. Choi, Bull. Korean
Chem. Soc., 2002, 23, 149; (b) A. L. Tornesello, M.
Sanseverion, F. M. Buonaguro, Molecules, 2016, 21, 736.
12 P. Strazzolini, A. G. Giumanini, S. Cauci, Tetrahedron, 1990,
46, 1081.
Conclusions
In conclusion, we developed an oxidant‐ and metal‐free synthetic
method for N‐formylation of amines by using N‐formyl imide under
catalysis with commercially available TsOH・H2O in water. Moreover,
we developed an efficient green protocol to prepare N‐formyl imides
by using acylamidines in the presence of TsOH ・ H2O in water.
Furthermore, N‐formyl imide can be used as a carbon source reagent
for constructing heterocycle motifs, such as benzimidazoles and
quinazolinones. Regarding the overall design, the key advantages are
(i) environmentally benign; (ii) can react under mild reaction
conditions without the use of oxidants or expensive metal catalysts;
and (iii) moderate to excellent reaction yield.
13 (a) R. A. Swaringen, J. F. Eaddy, T. R. Henderson, J. Org.
Chem., 1980, 45, 3986; (b) B. Kaboudin, M. Khodamorady,
Synlett, 2010, 2905.
14 A. R. Katritzky, H.-X. Chang, B. Yang, Synthesis, 1995, 503.
15 For selected examples with metal: (a) L. Becerra-Figueroa, A.
Ojeda-Porras, D. Gamba-Sanchez, J. Org. Chem., 2014, 79
,
4544; (b) M. Nirmala, G. Prakash, P. Viswanathamurthi, J. G.
Malecki, J. Mol. Catal. A: Chem., 2015, 403, 15; (c) D.-W. Gu,
X.-X. Guo, Tetrahedron, 2015, 71, 9117; (d) R. B. Sonawane,
N. K. Rasal, S. V. Jagtap, Org. Lett., 2017, 19, 2078; (e) H.
Sheng, R. Zeng, W. Wang, S. Luo, Y. Feng, J. Liu, W. Chen,
M. Zhu, Q. Guo, Adv. Synth. Catal., 2017, 359, 302. For
selected examples under transition metal-free conditions: (f) T.
Conflicts of interest
There are no conflicts of interest to declare.
Acknowledgements
M. El Dine, D. Evans, J. Rouden, J. Blanchet, Chem. Eur. J.
,
2016, 22, 5894; (g) J.-W. Wu, Y.-D. Wu, J.-J. Dai, H.-J. Xu,
Adv. Synth. Catal., 2014, 356, 2429; (h) T. B. Nguyen, J. Sorres,
This work is supported by grants from the Ministry of Science
and Technology, Taiwan (Grant MOST 108‐2113‐M‐005‐019‐).
We also thank for the support from the National Chung Hsing
University.
M. Q. Tran, L. Ermolenko, and A. Al-Mourabit Org. Lett.
,
2012, 14, 3202.
16 For selected examples with metal: (a) M. Hosseini-Sarvari, H.
Sharghi, J. Org. Chem., 2006, 71, 6652; (b) B. Karimi, F.
Mansouri, H. Vali, ChemPlusChem, 2015, 80, 1750; (c) S.
Kazemi, A. Mobinikhaledi, M. Zendehdel, Chin. Chem. Lett.
,
2017, 28, 1767. For selected examples under transition metal-
free conditions: (d) G. Brahmachari, S. Laskar, Tetrahedron
Lett., 2010, 51, 2319; (e) M. Lei, L. Ma, L. Hu Tetrahedron
Lett., 2010, 51, 4186; (f) J.-G. Kim, D. O. Jang, Synlett, 2010,
2093.
Notes and references
1
For selected examples: (a) F. Campos, M. P. Bosch, A.
Guerrero, Tetrahedron: Asymmetry, 2000, 11, 2705; (b) G. Ma,
M. Zancanella, Y. Oyola, R. D. Richardson, J. W. Smith, D.
17 For selected an example with metal: (a) X. Dong, Z. Wang, Y.
Duan, Y. Yang, Chem. Commun., 2018, 54, 8913. For selected
examples under transition metal-free conditions: (b) K. P.
Dhake, P. J. Tambade, R. S. Singhal, B. M. Bhanage, Green
Romo, Org. Lett., 2006, 8, 4497; (c) J. R. Dunetz, J. Magano,
G. A. Weisenburger, Org. Process Res. Dev., 2016, 20, 140;
(d) H. Lundberg, F. Tinnis, N. Selander, H. Adolfsson, Chem.
Soc. Rev., 2014, 43, 2714.
Chem
. Lett. Rev., 2011, 4, 151; (c) R. E. Patre, S. Mal, P. R.
Nikanth, S. K. Ghorai, S. H. Deshpande, M. E. Qacemi, T.
2
3
C. J. Gerack, L. McElwee-White, Molecules, 2014, 19, 7689.
(a) B. D. Barve, Y.-C. Wu, M. El-Shazly, D.-W. Chuang, Y.-
M. Chung, T.-H. Tsai, S.-F. Wu, M. Korinek, Y.-C. Du, C.-T.
Hsieh, J.-J. Wang, F.-R. Chang, Eur. J. Org. Chem., 2012,
6760; (b) N. V. Reddy, K. R. Prasad, P. S. Reddy, M. L.
Kantam, K. R. Reddy, Org. Biomol. Chem., 2014, 12, 2172.
(a) T. Kondo, S. Kotachi, Y. Tsuji, Y. Watanabe, T.-a. Mitsudo,
Organometallics, 1997, 16, 2562; (b) V. Krishnakumar, B.
Chatterjee, C. Gunanathan, Inorg. Chem., 2017, 56, 7278.
(a) A. Schnyder, M. Beller, G. Mehltretter, T. Nsenda, M.
Studer, A. F. Indolese, J. Org. Chem., 2001, 66, 4311; (b) Y.
Smejkal, S. Pal, B. N. Manjunath, Chem. Commun., 2017, 53
2382. (d) S. Batuta, N. A. Begum, Synth. Commun., 2017, 47
137.
,
,
18 (a) N. Ortega, C. Richter, F. Glorius, Org. Lett., 2013, 15, 1776;
(b) S. Tanaka, T. Minato, E. Ito, M. Hara, Y. Kim, Y.
Yamamoto, N. Asao, Chem. Eur. J., 2013, 19, 11832; (c) S.
Chakraborty, U. Gellrich, Y. Diskin-Posner, G. Leitus, L.
Avram, D. Milstein, Angew. Chem. Int. Ed., 2017, 56, 4229;
(d) B. Kang, S. H. Hong, Adv. Synth. Catal., 2015, 357, 834;
4
5
6 | J. Name., 2012, 00, 1‐3
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