4
Tetrahedron
9.
a) Meng, C.; Yang, K.; u, X.; Yuan, F. R. ACS Catal. 2015, 5,
3760-3766; (b) Abedi, S.; Morsali, A. ACS Catal. 2014, 4, 1398-
1403; (c) Lang, X.; Ma, W.; Chen, C.; Ji, H.; Zhao, J. Acc. Chem.
Res. 2014, 47, 355-363; (d) Zhang, M.; Wang, Q.; Chen, C.; Zang,
L.; Ma, W.; Zhao, J. Angew. Chem. Int. Ed. 2009, 48, 6081-6084.
In conclusion we have developed a highly chemoselective
photocatalytic strategy for oxidation of benzylic/allylic alcohols
to corresponding carbonyls. Cheap and easily available catalytic
system comprising of Eosin Y and TBHP was used. The method
not only obviates the use of toxic metal catalysts, but also high
energy light sources. The reaction is easily extendable to primary
as well as secondary benzyl alcohols having diverse set of
electron withdrawing as well as donating functions at room
temperature maintaining high selectivity. Furthermore, the
reaction can easily be upscaled to gram levels.
10. Muhldorf, B.; Wolf, R. Angew. Chem. Int. Ed. Engl. 2016, 55,
427-430.
11. Walsh, K.; Sneddon, H. F.; Moody, C. J. Org. Lett. 2014, 16,
5224-5227.
12. Adams, J. P.; Alder, C. M.; Andrews, I.; Bullion, A. M.;
Campbell-Crawford, M.; Darcy, M. G.; Hayler, J. D.; Henderson,
R. K.; Oare, C. A.; Pendrak, I.; Redman, A. M.; Shuster, L. E.;
Sneddon, H. F.; Walker, M. D. Green Chem. 2013, 15, 1542-1549.
13. (a) Hari, D. P.; Schroll, P.; Konig, B. J. Am. Chem. Soc. 2012,
134, 2958-2961; (b) Hari, D. P.; Konig, B. Chem. Commun. 2014,
50, 6688-6699; (c) Zhong, J.-J.; Meng, Q.-Y.; Liu, B.; Li, X.-B.;
Gao, X.-W.; Lei, T.; Wu, C.-J.; Li, Z.-J.; Tung, C.-H.; Wu, L.-Z.
Org. Lett. 2014, 16, 1988-1991; (d) Majek, M.; Filace, F.; von
Wangelin, A. J. Beilstein J. Org. Chem. 2014, 10, 981–989; (e)
Meyer, A. U.; Slanina, T. Å.; Yao, C.-J.; Konig, B. ACS Catalysis
2016, 6, 369-375.
Acknowledgments
We thank DST (SB/S1/OC-07/2013), New Delhi for financial
assistance. S. D thanks UGC India for research fellowship. BAS
thanks CSIR, India for Young Scientist Award. IIIM
Communication No. 1900.
14. a) Deshidi, R.; Kumar, M.; Devari, S. Shah, B. A. Chem.
Commun. 2014, 50, 9533-9535; (b) Devari, S.; Kumar, M.;
Deshidi, R.; Rizvi, M.; Shah, B. A. Beilstein J. Org. Chem. 2014,
10, 2649-2653; (c) Devari, S.; Kumar, A.; Deshidi, R.; Shah, B. A.
Chem. Commun. 2015, 51, 5013-5016; (d) Deshidi, R.; Devari, S.;
Shah, B. A. Org. Chem. Front. 2015, 2, 515; (e) Deshidi, R.;
Devari, S.; Shah, B. A. Eur. J. Org. Chem. 2015, 1428-1432; (f)
Kumar, M.; Devari, S.; Kumar, A.; Sultan, S.; Ahmed, Q. N.;
Rizvi, M.; Shah, B. A. Asian J. Org. Chem., 2015, 4, 438-441; (g)
Kumar, A.; Shah, B. A. Org. Lett. 2015, 17, 52325235; (h) Sultan,
S.; Kumar, M.; Devari, S.; Mukherjee, D.; Shah, B. A.
ChemCatChem 2016, 18, 703-707; (i) Devari, S.; Shah, B. A.
Chem. Commun. 2016, 52, 1490-1493.
References and notes
1.
a) Passiniemi, M.; Koskinen, A. M. Beilstein J. Org. Chem. 2013,
9, 2641-2659; (b) Baumann, M.; Baxendale, I. R. Beilstein J. Org.
Chem. 2013, 9, 2265-2319. (c) Ma, Y.-T.; Fan, H.-F.; Gao, Y.-Q.;
Li, H.; Zhang, A.-L.; Gao, J.-M. Chem. Biol. Drug Des. 2013, 81,
545-552; (d) Brown, P. D.; Willis, A. C.; Sherburn, M. S.;
Lawrence, A. L. Org. Lett. 2012, 14, 4537-4539; (e) Kouloura, E.;
Halabalaki, M.; Lallemand, M.-C.; Nam, S.; Jove, R.; Litaudon,
M.; Awang, K.; Hadi, H. A.; Skaltsounis, A.-L. J. Nat. Prod.
2012, 75, 1270-1276; (f) Chen, J.-J.; Cho, J.-Y.; Hwang, T.-L.;
Chen, I.-S. J. Nat. Prod. 2008, 71, 71-75; (g) Su, C.-R.; Kuo, P.-
C.; Wang, M.-L.; Liou, M.-J.; Damu, A. G.; Wu, T.-S. J. Nat.
Prod. 2003, 66, 990-993; (h) Lin, L.-C.; Chou, C.-J.; Chen, K.-T.;
Chen, C.-F. J. Nat. Prod. 1993, 56, 926-928.
15. a) Li, J.; Zhang, J.; Tan, H.; Wang, D. Z. Org. Lett. 2015, 17,
2522-2525; (b) Yang, W.; Yang, S.; Li, P.; Wang, L. Chem.
Commun. 2015, 51, 7520-7523.
16. General procedure for oxidation of alcohols: Oven dried round
bottom flask was charged with Eosin Y (5 mmol) alcohol (1
mmol) and 3 equiv. of TBHP (5.5M in decane) in dry ACN. The
resulting mixture was degassed for 15 mins, followed by back
filling N2, and then irradiated under Blue LED light (12W, 455
nm) at room temperature (25 oC). After reaction completion
monitored through TLC, the mixture was diluted with 15 ml of
10% NaHCO3 solution, and extracted with EtOAc (3 × 20 ml).
The combined organic extracts were washed with brine (20 ml),
dried over Na2SO4, and concentrated on vacuo. Purification of the
crude product on silica gel using EtOAc:Hexane as solvent system
afforded the desired product.
2.
3.
a) Chen, B.; Wang, L.; Gao, S. ACS Catal. 2015, 5, 5851-5876;
(b) Hoover, J. M.; Steves, J. E.; Stahl, S. S. Nat. Protocols 2012,
7, 1161-1166; (c) Parmeggiani, C.; Cardona, F. Green Chem.
2012, 14, 547-564; (d) Zhan, B.-Z.; Thompson, A. Tetrahedron
2004, 60, 2917-2935; (e) Matsumoto, T.; Ueno, M.; Wang, N.;
Kobayashi, S. Chem. Asian J. 2008, 3, 196-214; (f) Mallat, T.;
Baiker, A. Chem. Rev. 2004, 104, 3037-3058.
a) Manzini, S., Urbina-Blanco, C. S. A.; Nolan, S. P.
Organometallics 2013, 32, 660-664; (b) Hoover, J. M.; Stahl, S. S.
J. Am. Chem. Soc. 2011, 133, 16901-16910; (b) De Luca, L.;
Giacomelli, G.; Porcheddu, A. Org. Lett. 2001, 3, 3041-3043; (d)
Adam, W.; Hajra, S.; Herderich, M.; Saha-Moller, C. R. Org. Lett.
2000, 2, 2773-2776.
4.
5.
6.
7.
Wang, L.; Li, J.; Yang, H.; Lv, Y.; Gao, S. J Org Chem. 2012 77,
790-794.
Cosner, C. C.; Cabrera, P. J.; Byrd, K. M.; Thomas, A. M.;
Helquist, P. Org. Lett. 2011, 13, 2071-2073.
[6] Tripathi, C. B.; Mukherjee, S. J. Org. Chem. 2012, 77, 1592-
1598.
a) Rout, L.; Nath, P.; Punniyamurthy, T. Adv. Synth. Catal. 2007,
349, 846-848; (b) Hanson, S. K.; Wu, R.; pete Silks; L. A. Org.
Lett., 2011, 13, 1908-1911.
Supplementary Material
Experimental procedure, characterization data, 1H and 13C
NMR of relevant compounds.
Click here to remove instruction text...
8.
Devari, S.; Deshidi, R.; Kumar, M.; Kumar, A.; Sharma, S.;
Rizvi, M.; Kushwaha, M.; Gupta, A. P.; B. A. Shah, Tetrahedron
Lett. 2013, 54, 6407-6410.