family of tris(pyrazolyl)borate silver complexes and other unique silver complexes
were designed, synthesized, and characterized and further proved to be efficient
catalysts in this field. Fascinating methodologies were developed for functionalization of different aliphatic C–H bonds, particularly, methane and short alkanes
with EDA by perfluorinated tris(pyrazolyl)borate silver complexes in scCO 2 . Silver-catalyzed/silver-mediated sp
3 C–H amination/amidation, difluorination, and
trifluoromethylthiolation provided a great potential for future late-stage functionalization of pharmaceutical and agrochemical compounds. All these developments
will blossom a new field to approach the direct aliphatic C–H functionalization. As
a cheap noble metal, silver exhibited an exciting feature in catalysis, tunable by the
different ligands. We believe that silver will play more and more important roles in
direct C–H functionalization with the development of new processes.
Acknowledgment Financial support by MOST (2015CB856600 and 2013CB228102) and NSFC
(Nos. 21332001 and 21431008) is gratefully acknowledged. T.Z. was supported in part by the
Postdoctoral Fellowship of Peking-Tsinghua Center for Life Sciences and China Postdoctoral
Science Foundation Grant (2014 M550546).
References
1. Ladd CL, Sustac Roman D, Charette AB (2013) Org Lett 15:1350
2. Maestre L, Sameera WMC, Dı ´az-Requejo MM, Maseras F, Pe ´rez PJ (2013) J Am Chem Soc
135:1338
3. Naodovic M, Yamamoto H (2008) Chem Rev 108:3132
4. Yanagisawa A, Takeshita S, Izumi Y, Yoshida K (2010) J Am Chem Soc 132:5328
5. Li Z, He C (2006) Eur J Org Chem 2006:4313
6. A ´ lvarez-Corral M, Mu~ noz-Dorado M, Rodrı ´guez-Garcı ´a I (2008) Chem Rev 108:3174
7. Yamamoto Y (2008) Chem Rev 108:3199
8. Dias HVR, Lovely CJ (2008) Chem Rev 108:3223
9. Dı ´ez-Gonza ´lez S, Nolan SP (2008) Acc Chem Res 41:349
10. Munoz MP (2014) Chem Soc Rev 43:3164
11. Weibel J-M, Blanc A, Pale P (2008) Chem Rev 108:3149
12. Harmata M (ed) (2010) Silver in organic chemistry. Wiley, Hoboken
13. Cheng C, Hartwig JF (2015) Chem Rev. doi:10.1021/cr5006414
14. Burgess K, Lim H-J, Porte AM, Sulikowski GA (1996) Angew Chem Int Ed 35:220
15. Doyle MP (2011) ChemCatChem 3:1681
16. Pe ´rez PJ (ed) (2012) Alkane C–H activation by single-site metal catalysis. Springer,
Netherlands
17. Rangan K, Fianchini M, Singh S, Dias HVR (2009) Inorg Chim Acta 362:4347
18. Dias HVR, Browning RG, Richey SA, Lovely CJ (2004) Organometallics 23:1200
19. Dias HVR, Browning RG, Richey SA, Lovely CJ (2005) Organometallics 24:5784
20. Urbano J, Belderraı ´n TR, Nicasio MC, Trofimenko S, Dı ´az-Requejo MM, Pe ´rez PJ (2005)
Organometallics 24:1528
21. Despagnet-Ayoub E, Jacob K, Vendier L, Etienne M, A ´ lvarez E, Caballero A, Dı ´az-Requejo
MM, Pe ´rez PJ (2008) Organometallics 27:4779
22. Caballero A, Despagnet-Ayoub E, Mar Dı ´az-Requejo M, Dı ´az-Rodrı ´guez A, Gonza ´lez-Nu ´~ nez
ME, Mello R, Mu~ noz BK, Ojo W-S, Asensio G, Etienne M, Pe ´rez PJ (2011) Science 332:835
130
T. Zhou and Z.-J. Shi
were designed, synthesized, and characterized and further proved to be efficient
catalysts in this field. Fascinating methodologies were developed for functionalization of different aliphatic C–H bonds, particularly, methane and short alkanes
with EDA by perfluorinated tris(pyrazolyl)borate silver complexes in scCO 2 . Silver-catalyzed/silver-mediated sp
3 C–H amination/amidation, difluorination, and
trifluoromethylthiolation provided a great potential for future late-stage functionalization of pharmaceutical and agrochemical compounds. All these developments
will blossom a new field to approach the direct aliphatic C–H functionalization. As
a cheap noble metal, silver exhibited an exciting feature in catalysis, tunable by the
different ligands. We believe that silver will play more and more important roles in
direct C–H functionalization with the development of new processes.
Acknowledgment Financial support by MOST (2015CB856600 and 2013CB228102) and NSFC
(Nos. 21332001 and 21431008) is gratefully acknowledged. T.Z. was supported in part by the
Postdoctoral Fellowship of Peking-Tsinghua Center for Life Sciences and China Postdoctoral
Science Foundation Grant (2014 M550546).
References
1. Ladd CL, Sustac Roman D, Charette AB (2013) Org Lett 15:1350
2. Maestre L, Sameera WMC, Dı ´az-Requejo MM, Maseras F, Pe ´rez PJ (2013) J Am Chem Soc
135:1338
3. Naodovic M, Yamamoto H (2008) Chem Rev 108:3132
4. Yanagisawa A, Takeshita S, Izumi Y, Yoshida K (2010) J Am Chem Soc 132:5328
5. Li Z, He C (2006) Eur J Org Chem 2006:4313
6. A ´ lvarez-Corral M, Mu~ noz-Dorado M, Rodrı ´guez-Garcı ´a I (2008) Chem Rev 108:3174
7. Yamamoto Y (2008) Chem Rev 108:3199
8. Dias HVR, Lovely CJ (2008) Chem Rev 108:3223
9. Dı ´ez-Gonza ´lez S, Nolan SP (2008) Acc Chem Res 41:349
10. Munoz MP (2014) Chem Soc Rev 43:3164
11. Weibel J-M, Blanc A, Pale P (2008) Chem Rev 108:3149
12. Harmata M (ed) (2010) Silver in organic chemistry. Wiley, Hoboken
13. Cheng C, Hartwig JF (2015) Chem Rev. doi:10.1021/cr5006414
14. Burgess K, Lim H-J, Porte AM, Sulikowski GA (1996) Angew Chem Int Ed 35:220
15. Doyle MP (2011) ChemCatChem 3:1681
16. Pe ´rez PJ (ed) (2012) Alkane C–H activation by single-site metal catalysis. Springer,
Netherlands
17. Rangan K, Fianchini M, Singh S, Dias HVR (2009) Inorg Chim Acta 362:4347
18. Dias HVR, Browning RG, Richey SA, Lovely CJ (2004) Organometallics 23:1200
19. Dias HVR, Browning RG, Richey SA, Lovely CJ (2005) Organometallics 24:5784
20. Urbano J, Belderraı ´n TR, Nicasio MC, Trofimenko S, Dı ´az-Requejo MM, Pe ´rez PJ (2005)
Organometallics 24:1528
21. Despagnet-Ayoub E, Jacob K, Vendier L, Etienne M, A ´ lvarez E, Caballero A, Dı ´az-Requejo
MM, Pe ´rez PJ (2008) Organometallics 27:4779
22. Caballero A, Despagnet-Ayoub E, Mar Dı ´az-Requejo M, Dı ´az-Rodrı ´guez A, Gonza ´lez-Nu ´~ nez
ME, Mello R, Mu~ noz BK, Ojo W-S, Asensio G, Etienne M, Pe ´rez PJ (2011) Science 332:835
130
T. Zhou and Z.-J. Shi