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CC BY-ND-NC 4.0 · Synthesis 2019; 51(05): 1207-1215
DOI: 10.1055/s-0037-1611646
DOI: 10.1055/s-0037-1611646
feature
Alkali Metal Effects in Trans-Metal-Trapping (TMT): Comparing LiTMP with NaTMP in Cooperative MTMP/Ga(CH2SiMe3)3 Metalation Reactions
We thank the European Research Council (ERC StG, MixMetApps) and the EPSRC (EP/N011384/1) for their generous sponsorship of this research.Further Information
Publication History
Received: 30 November 2018
Accepted: 05 December 2018
Publication Date:
15 January 2019 (online)
![](https://www.thieme-connect.de/media/synthesis/201905/lookinside/thumbnails/ss-2018-z0802-fa_10-1055_s-0037-1611646-1.jpg)
Published as part of the 50 Years SYNTHESIS – Golden Anniversary Issue
Abstract
Stepwise metalation and trapping, so called trans-metal-trapping (TMT), of anisole is studied using LiTMP as base and Ga(CH2SiMe3)3 as trap. The isolated ‘trapped’ intermediate is also assessed in C–C bond forming reactions, highlighting the inherent advantages and remaining challenges of this system. The same base trap mixture is found to metallate N–Me bonds of the diamines TMEDA and PMDETA. Comparative studies replacing LiTMP by NaTMP have found significant alkali metal effects on the extent of both base-trap cocomplexation and onward reactivities of TMT products.
Key words
metalation - gallium trans-metal-trapping - carbanions - cooperative effects - lithium - sodiumSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1611646.
- Supporting Information
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References
- 1a Clayden J. In Organolithiums: Selectivity for Synthesis 2002
- 1b Snieckus V. Chem. Rev. 1990; 90: 879
- 1c Mongin F, Schlosser M. Tetrahedron Lett. 1996; 37: 6551
- 1d Schlosser M. Angew. Chem. Int. Ed. 2005; 44: 376
- 1e Werner V, Klatt T, Fujii M, Markiewicz J, Apeloig Y, Knochel P. Chem. Eur. J. 2014; 20: 8338
- 1f Mulvey RE, Robertson SD. Angew. Chem. Int. Ed. 2013; 52: 11470
- 2 Becker MR, Knochel P. Angew. Chem. Int. Ed. 2015; 54: 12501
- 3a Schlosser M. J. Organomet. Chem. 1967; 8: 9
- 3b Lochmann L, Pospisil J, Lim D. Tetrahedron Lett. 1966; 7: 257
- 4a Wunderlich SH, Rohbogner CJ, Unsinn A, Knochel P. Org. Process Res. Dev. 2010; 14: 339
- 4b Haag B, Mosrin M, Ila H, Malakhov V, Knochel P. Angew. Chem. Int. Ed. 2011; 50: 9794
- 5a Uchiyama M, Kameda M, Mishima O, Yokoyama N, Koike M, Kondo Y, Sakamoto T. J. Am. Chem. Soc. 1998; 120: 4934
- 5b Kondo Y, Shilai M, Uchiyama M, Sakamoto T. J. Am. Chem. Soc. 1999; 121: 3539
- 5c Snégaroff K, Komagawa S, Chevallier F, Gros PC, Golhen S, Roisnel T, Uchiyama M, Mongin F. Chem. Eur. J. 2010; 16: 8191
- 5d Akimoto G, Otsuka M, Takita R, Uchiyama M, Hedidi M, Bentabed-Ababsa G, Lassagne F, Erb W, Mogin F. J. Org. Chem. 2018; 83: 13498
- 6a Mulvey RE, Mongin F, Uchiyama M, Kondo Y. Angew. Chem. Int. Ed. 2007; 46: 3802
- 6b Andrikopoulos PC, Armstrong DR, Graham DV, Hevia E, Kennedy AR, Mulvey RE, O’Hara CT, Talmard C. Angew. Chem. Int. Ed. 2005; 44: 3459
- 6c Armstrong DR, Clegg W, Dale SH, Graham DV, Hevia E, Hogg LM, Honeyman GW, Kennedy AR, Mulvey RE. Chem. Commun. 2007; 598
- 6d Clegg W, Conway B, Graham DV, Hevia E, Kennedy AR, Mulvey RE, Russo L, Wright DS. Chem. Eur. J. 2009; 15: 7074
- 6e Armstrong DR, Blair VL, Clegg W, Dale SH, Garcia-Alvarez J, Honeyman GW, Hevia E, Mulvey RE, Russo L. J. Am. Chem. Soc. 2010; 132: 9480
- 6f Wunderlich SH, Kienle M, Knochel P. Angew. Chem. Int. Ed. 2009; 48: 7256
- 6g Garcia-Álvarez J, Kennedy AR, Klett J, Mulvey RE. Angew. Chem. Int. Ed. 2007; 46: 1105
- 6h Blair VL, Clegg W, Conway B, Hevia E, Kennedy AR, Klett J, Mulvey RE, Russo L. Chem. Eur. J. 2008; 14: 65
- 6i Wunderlich SH, Knochel P. Angew. Chem. Int. Ed. 2009; 48: 9717
- 6j Alborés P, Carrella LM, Clegg W, García-Álvarez P, Kennedy AR, Klett J, Mulvey RE, Rentschler E, Russo L. Angew. Chem. Int. Ed. 2009; 48: 3317
- 6k Nagaradja E, Chevallier F, Roisnel T, Jouikov V, Mongin F. Tetrahedron 2012; 68: 3063
- 6l Bedford RB, Brenner PB, Carter E, Cogswell PM, Haddow MF, Harvey JN, Murphy DM, Nunn J, Woodall CH. Angew. Chem. Int. Ed. 2014; 53: 1804
- 6m Martínez-Martínez AJ, Kennedy AR, Mulvey RE, O’Hara CT. Science (Washington, D. C.) 2014; 346: 834
- 7a Armstrong DR, Crosbie E, Hevia E, Mulvey RE, Ramsay DL, Robertson SD. Chem. Sci. 2014; 5: 3031
- 7b Uzelac M, Kennedy AR, Hevia E. Inorg. Chem. 2017; 56: 8615
- 7c Uzelac M, Mulvey RE. Chem. Eur. J. 2018; 24: 7786
- 8a Uzelac M, Kennedy AR, Hevia E, Mulvey RE. Angew. Chem. Int. Ed. 2016; 55: 13147
- 8b McLellan R, Uzelac M, Kennedy AR, Hevia E, Mulvey RE. Angew. Chem. Int. Ed. 2017; 56: 9566
- 9 Frischmuth A, Fernández M, Barl NM, Achrainer F, Zipse H, Berionni G, Mayr H, Karaghiosoff K, Knochel P. Angew. Chem. Int. Ed. 2014; 53: 7928
- 10 Armstrong DR, Brammer E, Cadenbach T, Hevia E, Kennedy AR. Organometallics 2013; 32: 480
- 11 Hevia E, Kennedy AR, Mulvey RE, Ramsay DL, Robertson SD. Chem. Eur. J. 2013; 19: 14069
- 12 Kramer MU, Robert D, Nakajima Y, Englert U, Spaniol TP, Okuda J. Eur. J. Inorg. Chem. 2007; 665
- 13 Hallock RB, Hunter WE, Atwood JL, Beachley OT. Jr. Organometallics 1985; 4: 547
- 14a Han Y, Fang L, Tao W.-T, Huang Y.-Z. Tetrahedron Lett. 1995; 36: 1287
- 14b Blum J, Gelman D, Baidossi W, Shakh E, Rosenfeld A, Aizenshtat Z, Wassermann BC, Frick M, Heymer B, Schutte S, Wernik S, Schumann H. J. Org. Chem. 1997; 62: 8681
- 14c Gelman D, Schumann H, Blum J. Tetrahedron Lett. 2000; 41: 7555
- 14d Mikami S, Yorimitsu H, Oshima K. Synlett 2002; 1137
- 15 Dennis LM, Patnode W. J. Am. Chem. Soc. 1932; 54: 182
- 16a Sheldrick GM. Acta Crystallogr., Sect. C 2015; 71: 3
- 16b Dolomanov OV, Bourhis LJ, Gildea RJ, Howard JA. K, Puschmann H. J. Appl. Crystallogr. 2009; 42: 339
- 17 Kohn W, Becke AD, Parr RG. J. Phys Chem. 1996; 100: 12974
- 18 Becke AD. Phys. Rev. A. 1988; 38: 3098
- 19 Lee C, Yang W, Parr RG. Phys. Rev. B. 1988; 37: 785
- 20 McLean AD, Chandler GS. J. Chem. Phys. 1980; 72: 5639
- 21 Alam N, Amatore C, Combellas C, Pinson J, Savéant J.-M, Thiébault A, Verpeaux J.-N. J. Org. Chem. 1988; 53: 1496
- 22 Jafarpour F, Rashidi-Ranjbar P, Kashani AO. Eur. J. Org. Chem. 2011; 2128
- 23 Kulbitski K, Nisnevich G, Gandelman M. Adv. Synth. Catal. 2011; 353: 1438