RSC Advances
Page 4 of 5
DOI: 10.1039/C5RA10552H
Further reduction using Lithium Aluminium hydride (LAH) of
the cyanated derivative in dry diethyl ether gave the ꢀPMP
8
9
(a) A. Wagner, W. Han, P. Mayer, A.R. Ofial, Adv. Synth.
Catal., 2013, 355, 3058; D. Verma, S. Verma, A. K. Sinha,
S.L. Jain, ChemPlusChem, 2013, 78, 860.
N
protected diamine derivative in 63% yield and the final overall
yield for the two steps is 74% (Scheme 3).24 Finally, we have
succeeded in applying the cyanation methodology developed by
us for the formal synthesis of Praziquantel. Further studies to
elucidate the mechanism of the reaction and to utilise the
methodology for the synthesis of various natural products, drug
molecules is being pursued in our group.
(a) T. Nobuta , N. Tada , A. Fujiya , A. Kariya , T. Miura , A.
Itoh, Org. Lett., 2013, 15, 574; (b) J. D. Kumar, M. Lamani, K.
Alagiri, K. R. Prabhu, Org. Lett., 2013, 15, 1092.
10 (a) P. Kumar, S. Varma, S. L. Jain, J. Mater. Chem. A, 2014,
, 4514; (b) M. Rueping, S. Zhu, R. M. Koenigs Chem.
2
Commun., 2011, 47, 12709.
In conclusion we have developed a recyclable protocol
11 H. Ueda, K. Yoshida, H. Tokuyama, Org. Lett., 2014, 16,
for the
α
ꢀcyanation of amines by a CDC reaction under acid
4194.
free conditions using benign and affordable Iron oxide
nanoparticles in combination with a user friendly cyanide
source ꢀ ethyl cyanoformate. The mild reaction conditions and
recyclability of the catalyst makes this a sustainable protocol
12 C. Yan, Y. Liu, Q. Wang, RSC Adv. 2014, 4, 60075.
13 For recent reviews, books and articles on magnetically
recoverable catalysts and nanocatalysis please refer these and
the references cited therein (a) B. Karimi, F. Mansouri, H. M.
Mirzaei, ChemCatChem 2015, doi 10.1002/cctc.201403057;
for the synthesis of αꢀcyanated amines. Also the formal total
synthesis of the antiꢀSchistosomiasis drug Praziquantel was
achieved with the developed cyanation method as the key step.
(b) R. B. N. Baig, R. S. Varma, Chem. Commun., 2013, 49
,
752; (c) M. B. Gawande, P. S. Branco, R. S. Varma, Chem.
Soc. Rev., 2013, 42, 3371; (d) V. Polshettiwar, R. Luque, A.
Fihri, H. Zhu, M. Bouhrara, J. M. Basset, Chem. Rev., 2011,
Acknowledgements
111, 3036; (e) C. W. Lim, I. S. Lee, Nano Today., 2010, 5,
The authors are grateful to SAIFꢀIITB for the providing
the TEM, ICPꢀAES and XRD analysis. MP is grateful to CSIR,
Govt. of India for the research fellowship. AVK is thankful to
DST, Govt. of India for the INSPIRE Faculty Award [IFA12ꢀ
CHꢀ40] and research funding. Institute of Chemical Technology
(ICT) is acknowledged for providing the research facilities.
412; (f) Nanocatalysis: Synthesis and Applications Edited by
V. Polishettiwar, T. Asefa, John Wiley & Sons Inc., Hoboken,
New Jersey, 2013; (g) Nanomaterials in Catalysis, Edited by
P. Serp, K. Philippot, WileyꢀVCH Verlag & Co. KGaA,
Weinheim, Germany, 2013.
14 The MOF structure disintegrated during the reaction.
15 L. Liu, Z. Wang, X. Fu, C.ꢀH. Yan, Org. Lett., 2012, 14, 5692.
16 (a) K. T. V. Rao, B. Haribabu, P. S. S. Prasad, N. Lingaiah,
Notes and references
Department of Chemistry, Institute of Chemical Technology, Matunga,
Mumbai, Maharashtra, India ꢀ 400019, Tel.No. (91) 2233612614; Fax
No. (91) 2233611020
ChemCatChem, 2012,
V. P. Reddy, B. S. P. A. Kumar, Y. V. D. Nageswar, RSC Adv.
2012, , 11084.
4, 1173; (b) K. H. V. Reddy, G. Satish,
2
†
Electronic Supplementary Information (ESI) available: Experimental
procedures, 1HꢀNMR, 13CꢀNMR for all compounds are available. See
DOI: 10.1039/b000000x/
17 D. P. Hari, B. König, Org. Lett., 2011, 13, 3852.
18 C. Zhang, C. Liu, Y. Shao, X. Bao, X. Wan, Chem. Eur. J.
2013, 19, 17917.
,
1
2
3
(a) C.J. Li, Acc. Chem. Res., 2009, 42, 335; (b) From C–H to
C–C Bonds CrossꢀDehydrogenativeꢀCoupling Edited by C.J.
Li, Royal Society of Chemistry, Cambridge, England, 2014,
331; (c) R. Yang, Q. Ruan, B.Y. Zhang, Z. L. Zheng, F. Miao,
L. Zhou, H. L. Geng, Molecules, 2014, 19, 8051.
19 A. Wagner, A. R. Ofial, J. Org. Chem., 2015, 80, 2848.
20 The Xꢀray diffraction pattern of nanocrystalline γꢀFe2O3 was
comparable with the XRD pattern reported in literature: T.
Hyeon, S. S. Lee, J. Park, Y. Chung, H. B. Na, J. Am. Chem.
Soc. 2001, 123, 12798
(a) S.ꢀI. Murahashi, N. Komiya, H. Terai, Angew. Chem.,
2005, 117, 7091; Angew. Chem. Int. Ed., 2005, 44, 6931; (b) S.
I. Murahashi, T. Nakae, H. Terai, N. Komiya, J. Am. Chem.
Soc. 2008, 130, 11005; (c) S. Verma, S. L. Jain, B. Sain,
21 Refer supporting information for IR of native and used
catalysts.
22 (a) P. Steinmann, J. Keiser, R. Bos, M. Tanner, J. Utzinger,
Lancet Infect. Dis., 2006, 6, 411; (b) C. R. Caffrey, Curr. Opin.
ChemCatChem 2011,
3, 1329.
Chem. Biol., 2007, 11, 433; (c) A.ꢀL. Chenine, E ShaiꢀKobiler,
L. N. Steele, H. Ong, P. Augostini, R. Song, S. J. Lee, P.
Autissier, R. M. Ruprecht, W. E. Secor, PLoS Neglected Trop.
(a) Z. Li, C.ꢀJ. Li, Eur. J. Org. Chem. 2005, 3173; (b) R.
Hudson, S. Ishikawa, C.J. Li, A. Moores, Synlett, 2013, 24
,
1637.
Dis., 2008,
Gynecolog. Surg.,2009,
Poggensee, Int. J. Std. AIDS, 1994,
2
, 265; (d) A. Alalade, S. Leeson, U. Andrady,
, 177; (e) H. Feldmeier, I. Krantz, G.
, 368; (f) E. F. Kjetland,
4
5
6
7
(a) S. Singhal, S. L. Jain, B. Sain, Chem. Commun., 2009, 17
,
6
237.
5
(a) Y. Zhang, H. Peng, M. Zhang, Y. Cheng, C. Zhu, Chem.
Commun., 2011, 47, 2354.
P. D. Ndhlovu, E. Gomo, T. Mduluza, N. Midzi, L. Gwanzura,
P. R. Mason, L. Sandvik, H. Friis, S. G. Gundersen, AIDS,
2006, 20, 593; (g) P. J. Hotez, A. Fenwick, E. F. Kjetland,
(a) K. Alagiri, K. R. Prabhu, Org. Biomol. Chem., 2012, 10
,
PLoS Neglected Trop. Dis., 2009,
Pohlke, F. Loebich, Experientia, 1977, 33, 1036; (i) T. M.
Bilharz, Z. wiss. Zool. 1853, , 53; (j) T. M. Bilharz, Wien.
3, e430; (h) J. Seubert, R.
835.
(a) N. Sakai, A. Mutsuro, R. Ikeda, T. Konakahara, Synlett
,
4
2013, 24, 1283.
RSC Adv.
This journal is © The Royal Society of Chemistry 2015