Please do not adjust margins
Green Chemistry
Page 4 of 6
DOI: 10.1039/C7GC02425H
COMMUNICATION
Journal Name
O
OH
O
Mahyari, M. S. Laeini, A. Shabani, Chem. Commun. 2014, 50, 7855. h) A.
Shaabani, M. Boroujeni, M. Laeini, Appl. Organometal. Chem. 2016, 30, 154.
X.-F. Zhao, C. Zhang, Synthesis 2007, 551.
H
OH
O
CO2
O
O
ꢀ
[5]
[6]
+ HCO3
O
O
O
O
O
a) L. Huang, K. Cheng, B. Yao, Y. Xie, Y. Zhang, J. Org. Chem. 2011, 76, 5732. b) A.
Stergiou, A. Bariotaki, D. Kalaitzakis, I. Smonou, J. Org. Chem. 2013, 78, 7268. c)
Z. Li, J. Yin, G. Wen, T. Li, X. Shen, RSC Adv. 2014, 4, 32298.
O
0.0 (0.0)
13.9 (4.1)
TS: 42.1 (19.5) DMSO
29.4 (31.2)
DMSO
∆G (∆E) in kcal/mol
[7]
[8]
[9]
a) G. Brahmachari, RSC Adv. 2016, 6, 64676. b) D. Ravelli, S. Protti, M. Fagnoni,
Chem. Rev. 2016, 116, 9850. c)
S
O
S
O
O
TS: 24.8 (21.6)
a) R. S. Menon, A. T. Biju, V. Nair, Beilstein J. Org. Chem. 2016, 12, 444. b) X.
Bugaut, F. Glorius, Chem. Soc. Rev. 2012, 41, 3511.
O
O
O
ꢀ
+ HCO3
O
O
O
O
O
O
a) Q. Liu, L. Wu, R. Jackstell, M. Beller, Nat. Commun. 2015, 6, 5933. b) F. D.
Bobbink, P. J. Dyson, J. Catal. 2016, 343, 52. c) P. G. Jessop, S. M. Mercer, D. J.
Heldebrant, Energy Environ. Sci. 2012, 5, 7240. d) N. Eghbali, C.-J. Li, Green
Chem. 2007, 9, 213. e) M. Peters, B. Köhler, W. Kuckshinrichs, W. Leitner,
ChemSusChem 2011, 4, 1216. f) T. G. Ostapowics, M. Schmitz, M. Krystof, J.
Klankermayer, W. Leitner, Angew. Chem. Int. Ed. 2013, 52, 12119. g) A.
Decortes, A. M. Castilla, A. W. Kleij, Angew. Chem. Int. Ed. 2010, 49, 9822.
DMS
H2O + CO2
ꢀ31.0 (ꢀ21.5)
22.3 (19.9)
25.1 (14.5)
Conclusions
In conclusion, we have demonstrated an efficient and sustainable
synthesis of symmetric and non-symmetric α-diketones directly from
aldehydes using CO2 as a promoter. This methodology has shown broad
substrates scope along with wide applications towards the synthesis of
pharmaceuticals and fine chemicals. Many of these α-diketones are
currently expensive or commercially not available but can easily be
accessed using our cheap and commercially available catalysts and
reagents. We believe this methodology could find interest in the
synthesis of highly functionalized molecules, in the synthesis of natural
products and pharmaceuticals.
[10] a) W. Desens, T. Werner, Adv. Synth. Catal. 2016, 358, 622. b) C. Kohrt, T.
Werner, ChemSusChem 2015, 8, 2031. c) S. Das, F. D. Bobbink, A. Gopakumar, P.
J. Dyson, Chimia, 2015, 69, 76.
[11] a) L. Wu, Q. Liu, I. Fleischer, R. Jackstell, M. Beller, Nat. Commun. 2014, 5, 3091;
b) S. Das, F. D. Bobbink, G. Laurenczy, P. J. Dyson, Angew. Chem. Int. Ed. 2014,
53, 12876. c) S. Das, F. D. Bobbink, S. Bulut, K. Soudani, P. J. Dyson, Chem.
Commun. 2016, 52, 2497. d) K. Sasano, J. Takaya, N. Iwasawa, J. Am. Chem. Soc.
2013, 135, 10954. e) H. Mizuno, J. Takaya, N. Iwasawa, J. Am. Chem. Soc. 2011,
133, 1251. f) C. M. Williams, J. B. Johnson, T. Rovis, J. Am. Chem. Soc. 2008, 130,
14396. g) S. Gaillard, C. S. J. Cazin, S. P. Nolan, Acc. Chem. Res. 2012, 45, 778. h)
I. I. F. Boogaerts, S. P. Nolan, J. Am. Chem. Soc. 2010, 132, 8858. i) X. Wang, M.
Nakajima, R. Martin, J. Am. Chem. Soc. 2015, 137, 8924. j) X. Wang, Y. Liu, R.
Martin, J. Am. Chem. Soc. 2015, 137, 647. k) C. D. N. Gomes, O. Jacquet, C.
Villiers, P. Thuery, M. Ephritikhine, T. Cantat, Angew. Chem. Int. Ed. 2012, 51,
187. l) D. Riemer, P. Hirapara, S. Das, ChemSusChem 2016, 9, 1916. m) M. Hulla,
F. D. Bobbink, S. Das, P. J. Dyson, ChemCatChem 2016, 8, 3338. n) S. Fenner, L.
Ackermann, Green. Chem. 2016, 18, 3804.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
[12] a) L. Zhang, Z. Wu, N. C. Nelson, A. D. Sadow, I. I. Slowing, S. H. Overbury, ACS
Catal. 2015, 5, 6426. b) M. B. Ansari, S.-E. Park, Energy. Environ. Sci. 2012, 5,
9419.
We thank Fonds der Chemischen Industrie (FCI, Liebig-Fellowship to
S.D.) for the financial support. We thank Georg-August-Universität
Göttingen start-up funding to support P.H. and N.H. We are also
thankful to Prof. Dr. Lutz Ackermann for his kind support behind our
work. Special support from Prof. Inke Siewert for GC measurements is
also acknowledged.
[13] a) X. Wang, Y. N. Lam, C. Lee, M. Ji, E. J. Kang, H. Jang, RSC Adv. 2013, 3, 24922.
b) L. Gu, Y. Zhang, J. Am. Chem. Soc. 2010, 132, 914. c) V. Nair, V. Varghese, R. R.
Paul, A. Jose, C. R. Sinu, R. S. Menon, Org. Lett. 2010, 12, 2653. d) P. –C. Chiang,
J. W. Bode, Org. Lett. 2011, 13, 2422. e) G. Pupo, R. Properzi, B. List, Angew.
Chem. Int. Ed. 2016, 55, 6099.
[14] a) S. N. Riduan, Y. Zhang, J. Y. Ying, Angew. Chem. Int. Ed. 2009, 48, 3322. b) F.
D. Bobbink, W. Gruszka, M. Hulla, S. Das, P. J. Dyson, Chem. Commun. 2016, 52,
10787.
Notes and references
[15] a) H. Irannejad, M. Amini, F. Khodagholi, N. Ansari, S. Tusi, M. Sharifzadeh, A.
Shafiee, Bioorg. Med. Chem. 2010, 18, 4224. b) Chen et al., ACS Med. Chem.
Lett. 2014, 5, 89.
[1]
a) K. C. Nicolaou, D. L. F. Gray, J. Tae, J. Am. Chem. Soc. 2004, 126, 613. b) X.
Hui, J. Desrivot, C. Bories, P. M. Loiseau, X. Franck, R. Hocquemiller, B. Figadère,
Bioorg. Med. Chem. 2006, 6, 815. c) G. R. Boyce, J. S. Johnson, Angew. Chem.
Int. Ed. 2010, 49, 8930.
[16] M. Gemayel, A. Narita, L. Dössel, R. Sundaram, A. Kiersnowski, W. Pisula, M.
Hansen, A. Ferrari, E. Orgiu, X. Feng, K. Müllen, P. Samori, Nanoscale 2014, 6,
6301.
[2]
a) C. A. Buehler, J. O. Harris, W. F. Arendale, J. Am. Chem. Soc. 1950, 72, 4953.
b) G. L. Southard, B. R. Zaborowsky, J. M. Pettee, J. Am. Chem. Soc. 1971, 93,
3303. c) S. Chen, Z. Liu, E. Shi, L. Chen, W. Wei, H. Li, Y. Cheng, X. Wan, Org. Lett.
2011, 13, 2274. d) Y. Xu, X. Wan, Tetrahedron Lett. 2013, 54, 642. e) M. S.
Yusybo, V. D. Filimonov, Synthesis, 1991, 131. f) W.-X. Lv, Y.-F. Zeng, S.-S. Zhang,
Q. Li, H. Wang, Org. Lett. 2015, 17, 2972.
[17] P. Gallezot, Chem. Soc. Rev. 2012, 41, 1538.
[18] a) J. Saranya, M. Sowmiya, P. Sounthary, K. Parameswari, S. Chitra, K.
Senthilkumar, J. Mol. Liq. 2016, 216, 42; b) P. Ghosh, A. Mandal, Green Chem.
Lett. Rev. 2012, 5, 127; c) P. Hu, Q. Wang, Y. Yan, S. Zhang, B. Zhang, Z. Wang,
Org. Biomol. Chem. 2013, 11, 4304; d) Q. Chen, V. Bryant, H. Lopez, D. Kelly, X.
Luo, A. Natarajan, Bioorg. Med. Chem. Lett. 2011, 21, 1929; e) S. Khaskar, M.
Alipour, Montash. Chem. 2013, 144, 395.
[3]
[4]
a) Z. Wan, C. D. Jones, D. Mitchell, J. Y. Pu, T. Y. Zhang, J. Org. Chem. 2005, 71,
826. b) W. Ren, Y. Xia, S.-J. Ji, Y. Zhang, X. Wan, J. Zhao, Org. Lett. 2009, 11,
1841. c) W. Ren, J. Liu, L. Chen, X. Wan, Adv. Synth. Catal. 2010, 352, 1424. d)
C.-F. Xu, M. Xu, Y.-X. Jia, C.-Y. Li, Org. Lett. 2011, 13, 1556. e) A. Gao, F. Yang, J.
Li, Y. Wu, Tetrahedron 2012, 68, 4950. f) J. Muzart, J. Mol. Catal. A: Chem. 2011,
338, 7. g) X. Zhu, P. Li, Q. Shi, L. Wang, Green Chem. 2016, 18, 6373.
[19] S. M. Lnagdon, M. M. D. Wilde, K. Thai, M. Gravel, J. Am. Chem. Soc. 2014, 136,
7539.
[20] Under nitrogen atmosphere we observed 1:1 ratio of mix cross benzoin
products together with homo products and then when we released CO2
atmosphere generated our desired product. We have observed the reactivity of
our catalyst in this following order: furfural>5-methyl furfural>HMF>Benzofuran
aldehyde. For the cross products formation, we took lowest reactive partner in
higher ratio than the highest reactive partner and that gave us the best yield
after examining all other possibilities. This ratio is highly important for the
selective formation of cross-products.
a) E. J. Steves, S. S. Stahl, J. Am. Chem. Soc. 2013, 135, 15742. b) Y. Yu, C. Lin, B.
Li, P. Zhao, S. Zhang, Green Chem. 2016, 18, 3647. c) G. Urgoitia, R. SanMartin,
M. T. Herrero, E. Domínguez, Green Chem. 2011,13, 2161. d) T. Bhattacharya, T.
K. Sarma, S. Samanta, Catal. Sci. Tech. 2012, 2, 2216. e) T. A. Alsalim, J. S. Hadi,
O. N. Ali, H. S. Abbo, S. J. Titinchi, Chem. Central J. 2013, 7, 2. f) M. Kirihara, Y.
Ochiai, S. Takizawa, H. Takahata, H. Nemoto, Chem. Commun. 1999, 1387. g) R.
Ray, S. Chandra, D. Maiti, G. K. Lahiri, Chem. Eur. J. 2016, 22, 8814. h) M.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins