Transition-Metal-Free, Potassium tert-Butoxide/Dimethyl Sulfoxide Mediated Amination between Tertiary Amines and Aryl Halides

Pei Huang; Bang-Yue He; Hui-Min Wang; Jian-Mei Lu

doi:10.1055/s-0034-1379367

Synthesis, Table of Contents

Synthesis 2015; 47(02): 221-227
DOI: 10.1055/s-0034-1379367

paper

Transition-Metal-Free, Potassium tert-Butoxide/Dimethyl Sulfoxide Mediated Amination between Tertiary Amines and Aryl Halides

Pei Huang

College of Chemistry and Materials Engineering, Wenzhou University, Chashan University Town, Wenzhou 325035, Zhejiang Province, P. R. of China Fax: +86(577)86689300 Email: ljm@wzu.edu.cn

,

Bang-Yue He

College of Chemistry and Materials Engineering, Wenzhou University, Chashan University Town, Wenzhou 325035, Zhejiang Province, P. R. of China Fax: +86(577)86689300 Email: ljm@wzu.edu.cn

,

Hui-Min Wang

College of Chemistry and Materials Engineering, Wenzhou University, Chashan University Town, Wenzhou 325035, Zhejiang Province, P. R. of China Fax: +86(577)86689300 Email: ljm@wzu.edu.cn

,

Jian-Mei Lu*

College of Chemistry and Materials Engineering, Wenzhou University, Chashan University Town, Wenzhou 325035, Zhejiang Province, P. R. of China Fax: +86(577)86689300 Email: ljm@wzu.edu.cn

› Author Affiliations

Abstract

All articles of this category

Abstract

A transition-metal-free, C–N bond-formation reaction between tertiary amines and aryl halides is reported. Under the optimal conditions, various aromatic and aliphatic tertiary amines react with aryl halides, including iodides, bromides, and chlorides, to give mono-aminated products, N,N-dialkylanilines and N-alkyl-N-arylanilines, in good to high yields. Based on the experimental results, the reaction is believed to occur via an aryne intermediate derived from the aryl halide.

Key words

transition-metal-free - tertiary amines - aryl halides - amination reaction - synthetic method

Full Text

References

References

1a Craig PN. Comprehensive Medicinal Chemistry . Vol. 8. Drayton CJ. Pergamon; Oxford: 1991
1b Belfield A, Brown GR, Foubister AJ. Tetrahedron 1999; 55: 11399
1c O’Hagan D. Nat. Prod. Rep. 2000; 17: 435
1d Amines: Synthesis, Properties, and Applications . Lawrence SA. Cambridge University Press; Cambridge: 2004
1e The Chemistry of Anilines . Rappoport Z. Wiley-VCH; Weinheim: 2007
1f Amino Group Chemistry: From Synthesis to the Life Sciences. Ricci A. Wiley-VCH; Weinheim: 2008

For some recent selected reviews, see:

2a Hartwig JF In Modern Arene Chemistry . Astruc D. Wiley-VCH; Weinheim: 2002: 107-168
2b Beletskaya IP, Averin AD. Pure Appl. Chem. 2004; 76: 1605
2c Hartwig JF. Acc. Chem. Res. 2008; 41: 1534
2d Surry DS, Buchwald SL. Angew. Chem. Int. Ed. 2008; 47: 6338
2e Lundgren RJ, Stradiotto M. Chem. Eur. J. 2012; 18: 9758
2f Bariwal J, Van der Eycken E. Chem. Soc. Rev. 2013; 42: 9283

3 For a recent review, see: Sambiagio C, Marsden SP, Blacker JA, McGowan PC. Chem. Soc. Rev. 2014; 43: 3525

4a Beller M, Breindl C, Riermeier T, Tillack A. J. Org. Chem. 2001; 66: 1403
4b Shi L, Wang M, Fan C.-A, Zhang F.-M, Tu Y.-Q. Org. Lett. 2003; 5: 3515
4c Narayan S, Seelhammer T, Gawley RE. Tetrahedron Lett. 2004; 45: 757
4d Kleist W, Pröckl SS, Drees M, Köhler K, Djakovitch L. J. Mol. Catal. A: Chem. 2009; 303: 15
4e Bolliger JL, Frech CM. Tetrahedron 2009; 65: 1180
4f Yuan Y, Thomé I, Kim SH, Chen D.-T, Beyer A, Bonnamour J, Zuidema E, Chang S, Bolm C. Adv. Synth. Catal. 2010; 352: 2892
4g Cano R, Ramón DJ, Yus M. J. Org. Chem. 2011; 76: 654
4h Thomé I, Bolm C. Org. Lett. 2012; 14: 1892
4i Chen C.-X, Chen C, Li B, Tao J.-W, Peng J.-S. Molecules 2012; 17: 12506 ; http://www.mdpi.com/journal/molecules
4j Baars H, Beyer A, Kohlhepp SV, Bolm C. Org. Lett. 2014; 16: 536

5a Ou L.-L, Shao J.-A, Zhang G.-L, Yu Y.-P. Tetrahedron Lett. 2011; 52: 1430
5b Xiao Q, Tian L.-M, Tan R.-C, Xia Y, Qiu D, Zhang Y, Wang J.-B. Org. Lett. 2012; 14: 4230
5c Zhui G.-Q, Ess DH, Falck JR, Kürti L. J. Am. Chem. Soc. 2012; 134: 18253
5d Coeffard V, Moreau X, Thomassigny C, Greck C. Angew. Chem. Int. Ed. 2013; 52: 5684

6a Liu Z.-J, Larock RC. Org. Lett. 2003; 5: 4673
6b Liu Z.-J, Larock RC. J. Org. Chem. 2006; 71: 3198

7a Carroll MA, Wood RA. Tetrahedron 2007; 63: 11349
7b Guo F.-L, Wang L.-M, Wang P.-Q, Yu J.-J, Han J.-W. Asian J. Org. Chem. 2012; 1: 218

8 In a preliminary paper, Wang and co-workers reported the transition-metal-free amination between aliphatic tertiary amines and aryl halides, see: Fang Y, Zheng Y.-Q, Wang Z.-Y. Eur. J. Org. Chem. 2012; 1495
9 In a preliminary communication, Biju and co-workers reported the transition-metal-free amination of aromatic tertiary amines with o-silylaryl triflates, see: Bhojgude SS, Kaicharla T, Biju AT. Org. Lett. 2013; 15: 5452

10a Huang P, Wang Y.-X, Yu H.-F, Lu J.-M. Organometallics 2014; 33: 1587
10b Chen W.-X, Zhang C.-Y, Shao L.-X. Tetrahedron 2014; 70: 880
10c Chen W.-X, Zhang C.-Y, Lu J.-M. J. Chem. Res. 2013; 611
10d Chen W.-X, Shao L.-X. J. Org. Chem. 2012; 77: 9236
10e Zhu L, Ye Y.-M, Shao L.-X. Tetrahedron 2012; 68: 2414
10f Zhu L, Gao T.-T, Shao L.-X. Tetrahedron 2011; 67: 5150

11 It should be noted here that KOt-Bu should be strictly dry (anhydrous), i.e. it is a very good powder with no bulky solid. If it contains some bulky solid, which maybe due to the hydrolysis of KOt-Bu, lower yield will be obtained. KOt-Bu was purchased from J&K Scientific Ltd. in 25-g packaging (99% purity). During our investigations we found that the reproducibility of different batches of such KOt-Bu was sufficient.
12 It is well established that the combination of a base and DMSO acts as a super base. For some selected papers, please see references 4f, 4g, and 8, and also: Baars H, Beyer A, Kohlhepp SV, Bolm C. Org. Lett. 2014; 16: 536
13 In the optimization procedure, it was found that the reaction could also be performed under air to give comparable yields, but the reproducibility was very poor. It seems that the reaction was sensitive to moisture, therefore all reactions were carried out under an atmosphere of N₂.

14a Bunnett JF, Zahler RE. Chem. Rev. 1951; 49: 273
14b March J. Advanced Organic Chemistry: Reactions, Mechanisms and Structure . 4th ed. John Wiley & Sons; New York: 1992: 641

For some recent selected reviews on arynes, see:

15a Dubrovskiy AV, Markina NA, Larock RC. Org. Biomol. Chem. 2013; 11: 191
15b Pérez D, Peña D, Guitián E. Eur. J. Org. Chem. 2013; 5981
15c Wu C.-R, Shi F. Asian J. Org. Chem. 2013; 2: 116
15d Tadross PM, Stoltz BM. Chem. Rev. 2012; 112: 3550
15e Gampe CM, Carreira EM. Angew. Chem. Int. Ed. 2012; 51: 3766
15f Bhunia A, Yetra SR, Biju AT. Chem. Soc. Rev. 2012; 41: 3140
15g Okuma K. Heterocycles 2012; 85: 515
15h Yoshida H, Takaki K. Synlett 2012; 23: 1725
15i Yoshida H, Ohshita J, Kunai A. Bull. Chem. Soc. Jpn. 2010; 83: 199
15j Chen Y, Larock RC. Arylation Reactions Involving the Formation of Arynes. In Modern Arylation Methods. Ackermann L. Wiley-VCH; Weinheim: 2009: 401
15k Sanz R. Org. Prep. Proced. Int. 2008; 40: 215

16 Hill LL, Moore LR, Huang R.-C, Cracium R, Vincent AJ, Dixon DA, Chou J, Woltermann CJ, Shaughnessy KH. J. Org. Chem. 2006; 71: 5117
17 Lipshutz BH, Chung DW, Rich B. Adv. Synth. Catal. 2009; 351: 1717
18 Hill LL, Crowell JL, Tutwilter SL, Massie NL, Hines CC, Griffin ST, Rogers RD, Shaughnessy KH. J. Org. Chem. 2010; 75: 6477
19 Xie X.-M, Zhang TY, Zhang Z.-G. J. Org. Chem. 2006; 71: 6522
20 Kokatla HP, Thomson PF, Bae S, Doddi VR, Lakshman MK. J. Org. Chem. 2011; 76: 7842
21 Park S, Brookhart M. J. Am. Chem. Soc. 2012; 134: 640
22 Lee Y.-H, Chen Y.-C, Hsieh J.-C. Eur. J. Org. Chem. 2012; 247

Supplementary Material

Supporting Information