Paper
RSC Advances
¨
newly formed –CH2OH group was either partially or fully 10 A. L. Muller, T. Bleith, T. Roth, H. Wadepohl and L. H. Gade,
etheried depending upon substrates. Plausible mechanisms of Organometallics, 2015, 34, 2326.
~
TH of carbonyl compounds under basic and base free condi- 11 A. H. Ngo, M. Ibanez and L. H. Do, ACS Catal., 2016, 6, 2637.
tions and etherication were proposed. The guanidinate 12 A. Ruff, C. Kirby, B. C. Chan and A. R. O'Connor,
ligands in the new complexes acts as a proton shuttle between
iPrOH and the carbonyl substrates in both base assisted and 13 K.-J. Haack, S. Hashiguchi, A. Fujii, T. Ikariya and R. Noyori,
base free TH. The presence of an in-built amido N atom in the Angew. Chem., Int. Ed. Engl., 1997, 36, 285.
guanidinato ligand of 3 does not necessitate the use of external 14 R. Noyori, M. Yamakawa and S. Hashiguchi, J. Org. Chem.,
base for successful base free TH. The dual nature of the gua- 2001, 66, 7931.
nidinato ligand in 3 as an acid and as a base in water elimi- 15 B. Zhao, Z. Han and K. Ding, Angew. Chem., Int. Ed., 2013, 52,
nation was ascribed for its successful role as catalyst in 4744.
etherication of the substrate such as 1-(hydroxymethyl)naph- 16 M. K. T. Tin, G. P. A. Yap and D. S. Richeson, Inorg. Chem.,
Organometallics, 2016, 35, 327.
thalene-2-ol.
1998, 37, 6728.
17 (a) P. J. Bailey and S. Pace, Coord. Chem. Rev., 2001, 214, 91;
(b) F. T. Edelmann, Adv. Organomet. Chem., 2013, 61, 55.
18 T. Singh, R. Kishan, M. Nethaji and N. Thirupathi, Inorg.
Chem., 2012, 51, 157.
Acknowledgements
We acknowledge the Department of Science and Technology,
Delhi for nancial support (Grant No: EMR/2014/000698) and 19 R. Kishan, R. Kumar, S. Baskaran, C. Sivasankar and
University Grant Commission for a fellowship (R. K.). We also
N. Thirupathi, Eur. J. Inorg. Chem., 2015, 3182.
acknowledge University Science Instrumentation Centre, 20 P. J. Bailey, L. A. Mitchell and S. Parsons, J. Chem. Soc.,
University of Delhi, Delhi 110 007 for infrastructural facilities Dalton Trans., 1996, 2839.
and NMR Research Centre, Indian Institute of Science, Banga- 21 M. B. Dinger, W. Henderson and B. K. Nicholson, J.
lore 560 012 for VT NMR measurements. The authors also thank Organomet. Chem., 1998, 556, 75.
Prof. R. Murugavel, Indian Institute of Technology, Bombay for 22 S. Aharonovich, M. Kapon, M. Botoshanski and M. S. Eisen,
the use of his single crystal X-ray diffraction facility for the Organometallics, 2008, 27, 1869.
structure determination of 8 established through a DAE-SRC 23 G. Ciancaleoni, C. Zuccaccia, D. Zuccaccia, E. Clot and
outstanding investigator award. Sophisticated Test and Instru-
A. Macchioni, Organometallics, 2009, 28, 960.
mentation Centre, Cochin University of Science and Tech- 24 (a) X. Wu and J. Xiao, in Comprehensive Organic Synthesis, ed.
nology, Cochin 682 022 is also acknowledged for elemental
analysis data for some compounds.
P. Knochel and G. A. Molander, Elsevier, Amsterdam, 2nd
edn, 2014, vol. 8, p. 198; (b) R. H. Morris, Chem. Rec., 2016,
16, 2644.
¨
25 (a) J. S. M. Samec, J.-E. Backvall, P. G. Andersson and
References
P. Brandt, Chem. Soc. Rev., 2006, 35, 237; (b) W. Baratta
and P. Rigo, Eur. J. Inorg. Chem., 2008, 4041.
26 M. Nordin, R.-Z. Liao, K. Ahlford, H. Adolfsson and F. Himo,
ChemCatChem, 2012, 4, 1095.
27 D. Wang and D. Astruc, Chem. Rev., 2015, 115, 6621.
28 H. G. Nedden, A. Zanotti-Gerosa and M. Wills, Chem. Rec.,
2016, 16, 2623.
¨
¨
1 R. Kramer, M. Maurus, K. Polborn, K. Sunkel, C. Robl and
W. Beck, Chem.–Eur. J., 1996, 2, 1518.
2 R. D. Simpson and W. J. Marshall, Organometallics, 1997, 16,
3719.
3 K. Murata and T. Ikariya, J. Org. Chem., 1999, 64, 2186.
4 (a) T. Ikariya, K. Murata and R. Noyori, Org. Biomol. Chem.,
2006, 4, 393; (b) T. Ikariya and A. J. Blacker, Acc. Chem. 29 S. Hashiguchi, A. Fujii, J. Takehara, T. Ikariya and R. Noyori,
Res., 2007, 40, 1300; (c) X. Wu, C. Wang and J. Xiao, J. Am. Chem. Soc., 1995, 117, 7562.
Platinum Met. Rev., 2010, 54, 3; (d) F. Foubelo, C. Najera 30 R. Castarlenas, M. A. Esteruelas and E. Onate,
and M. Yus, Tetrahedron: Asymmetry, 2015, 26, 769.
Organometallics, 2008, 27, 3240.
5 (a) A. J. Blacker, E. Clot, S. B. Duckett, O. Eisenstein, J. Grace, 31 (a) M. Kumar, J. DePasquale, N. J. White, M. Zeller and
´
˜
A. Nova, R. N. Perutz, D. J. Taylor and A. C. Whitwood, Chem.
Commun., 2009, 6801; (b) A. Nova, D. J. Taylor, A. J. Blacker,
S. B. Duckett, R. N. Perutz and O. Eisenstein,
Organometallics, 2014, 33, 3433.
E. T. Papish, Organometallics, 2013, 32, 2135; (b)
M. G. Sommer, S. Marinova, M. J. Kra, D. Urankar,
ˇ
D. Schweinfurth, M. Bubrin, J. Kosmrlj and B. Sarkar,
Organometallics, 2016, 35, 2840.
´
´
´
6 A. J. Blacker, S. B. Duckett, J. Grace, R. N. Perutz and 32 M. C. Carrion, F. Sepulveda, F. A. Jalon, B. R. Manzano and
´
A. M. Rodrıguez, Organometallics, 2009, 28, 3822.
A. C. Whitwood, Organometallics, 2009, 28, 1435.
7 M. Yadav, A. K. Singh and D. S. Pandey, Organometallics, 33 R. Kishan, PhD Thesis, University of Delhi, 2015.
2009, 28, 4713.
34 R. Kumar, PhD Thesis, University of Delhi, 2017.
8 A. Zamorano, N. Rendon, J. E. V. Valpuesta, E. Alvarez and 35 K. Li, J.-L. Niu, M.-Z. Yang, Z. Li, L.-Y. Wu, X.-Q. Hao and
E. Carmona, Inorg. Chem., 2015, 54, 6573. M.-P. Song, Organometallics, 2015, 34, 1170.
9 L. Casarrubios, M. A. Esteruelas, C. Larramona, 36 Y. Wei, J. Wu, D. Xue, C. Wang, Z. Liu, Z. Zhang, G. Chen and
´
´
´
~
J. G. Muntaner, M. Olivan, E. Onate and M. A. Sierra,
J. Xiao, Synlett, 2014, 25, 1295.
Organometallics, 2014, 33, 1820.
This journal is © The Royal Society of Chemistry 2017
RSC Adv., 2017, 7, 33890–33904 | 33903