Indium(III) Halides as New and Highly Efficient Catalysts for N-tert-Butoxycarbonylation of Amines

Sunay V. Chankeshwara; Asit K. Chakraborti

doi:10.1055/s-2006-942492

PAPER

Indium(III) Halides as New and Highly Efficient Catalysts for N-tert-Butoxycarbonylation of Amines

Sunay V. Chankeshwara, Asit K. Chakraborti*
National Institute of Pharmaceutical Education and Research (NIPER), Sector 67, S. A. S. Nagar, Punjab 160062, India
Fax: +91(172)2214692; e-Mail: akchakraborti@rediffmail.co; e-Mail: akchakraborti@niper.ac.in;

Abstract

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Abstract

Indium(III) bromide and chloride efficiently catalysed the N-tert-butoxycarbonylation of amines with (Boc)₂O at room temperature and under solvent-free conditions. Various aromatic, heteroaromatic and aliphatic amines were converted to N-tert-butylcarbamates in excellent yields in short times. Chiral amines, esters of α-amino acids and β-amino alcohols afforded optically pure N-t-Boc derivatives in high yields. The reactions were chemoselective and no competitive side reactions such as isocyanate, urea, and N,N-di-t-Boc formation were observed. Chemoselective conversion to N-tert-butylcarbamates took place with amino alcohols without any formation of oxazolidinones.

Key words

indium(III) halides - N-tert-butylcarbamates - amines - chiral α-amino acid esters - di-tert-butyl dicarbonate - chemoselectivity - solvent-free - room temperature

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References

1a Greene TW. Wuts PGM. Protecting Groups in Organic Synthesis 3rd ed.: Wiley; New York: 1999.

1b Theodoridis G. Tetrahedron 2000, 56: 2339

1c Sartori G. Ballini R. Bigi F. Bosica G. Maggi R. Righi P. Chem. Rev. 2004, 104: 199

2a Chakraborti AK. Gulhane R. Tetrahedron Lett. 2003, 44: 3521

2b Chakraborti AK. Gulhane R. Chem. Commun. 2003, 1896

2c Chakraborti AK. Gulhane R. Tetrahedron Lett. 2003, 44: 6749

2d Chakraborti AK. Sharma L. Gulhane R. . Tetrahedron 2003, 59: 7661

2e Chakraborti AK. Gulhane R. . Synlett 2003, 1805

2f Chakraborti AK. Gulhane R. . Synthesis 2004, 111

2g Chakraborti AK. Gulhane R. Synlett 2004, 627

3 Dilbeck GA. Field L. Gallo AA. Gargiulo RJ. J. Org. Chem. 1978, 43: 4593

4 Agami C. Couty F. Tetrahedron 2002, 58: 2701

5 Lutz C. Lutz V. Knochel P. Tetrahedron 1998, 54: 6385

6a Grehn L. Ragnarsson U. Angew. Chem., Int. Ed. Engl. 1984, 23: 296

6b Grehn L. Ragnarsson U. Angew. Chem., Int. Ed. Engl. 1985, 24: 510

6c Burk MJ. Allen JG. J. Org. Chem. 1997, 62: 7054

6d Basel Y. Hassner A. J. Org. Chem. 2000, 65: 6368

7a NaHCO₃ in MeOH under sonication: Einhorn J. Einhorn C. Luche J.-L. Synlett 1991, 37

7b Me₄NOH·5H₂O in MeCN: Khalil EM. Subasinghe NL. Johnson RL. Tetrahedron Lett. 1996, 37: 3441

7c NaHMDS in THF: Kelly TA. McNeil DW. Tetrahedron Lett. 1994, 35: 9003

7d Aqueous NaOH: Lutz C. Lutz V. Knochel P. Tetrahedron 1998, 54: 6385

7e K₂CO₃-Bu₄NI in DMF: Handy ST. Sabatini JJ. Zhang Y. Vulfova I. Tetrahedron Lett. 2004, 45: 5057

8 Guibé-Jampel E. Wakselman M. J. Chem. Soc., Chem. Commun. 1971, 267

9 Guibé-Jampel E. Wakselman M. Synthesis 1977, 772

10 Itoh M. Hagiwara D. Kamiya T. Tetrahedron Lett. 1975, 4393

11 Kim S. Lee JI. Chem. Lett. 1984, 237

12 Barcelo G. Senet J.-P. Sennyey G. Synthesis 1986, 627

13a Sweet DV. Registry of Toxic Effects of Chemical Substances 1985-86 US Govt. Printing Office; Washington DC: 1988. p.3336

13b Sweet DV. Registry of Toxic Effects of Chemical Substances 1985-86 US Govt. Printing Office; Washington DC: 1988. p.4049

14a Knölker H.-J. Braxmeier T. Tetrahedron Lett. 1996, 37: 5861

14b Knölker H.-J. Braxmeier T. Schlechtingen G. Angew. Chem., Int. Ed. Engl. 1995, 34: 2497

15 Darnbrough S. Mervic M. Condon SM. Burns CJ. Synth. Commun. 2001, 31: 3273

16 Pandey RK. Dagade SP. Upadhyay RK. Dongare MK. Kumar P. ARKIVOC 2002, vii: 28 ; www. arkat-usa.org

17 Bartoli G. Bosco M. Locatelli M. Marcantoni E. Massaccesi M. Melchiorre P. Sambri L. Synlett 2004, 1794

18 Sharma GVS. Reddy JJ. Lakshmi PS. Krishna PR. Tetrahedron Lett. 2004, 45: 6963

19 Heydari A. Hosseini SE. Adv. Synth. Catal. 2005, 347: 1129

20a Schumacher JC. Perchlorates - Their Properties, Manufacture and Uses, ACS Monograph Series Reinhold; New York: 1960.

20b Long J. Chem. Health Safety 2002, 9: 12

21 Chankeshwara SV. Chakraborti AK. Tetrahedron Lett. 2006, 47: 1087

22a Clark JH. Green Chem. 1999, 1

22b Tundo P. Anastas P. Black DS. Breen J. Collins T. Memoli S. Miyamoto J. Polyakoff M. Tumas W. Pure Appl. Chem. 2000, 72: 1207

23a Nair V. Ros S. Jayan CN. Pillai BS. Tetrahedron 2004, 60: 1959

23b Frost CG. Hartley JP. Mini-Rev. Org. Chem. 2004, 1: 1

23c Ranu BC. Eur. J. Org. Chem. 2000, 2347

23d Chauhan KK. Frost CG. J. Chem. Soc., Perkin Trans. 1 2000, 3015

24a Dondoni A. Perrone D. Semola T. Synthesis 1995, 181

24b Green R. Taylor PJM. Bull SD. James TD. Mahon MF. Merritt AT. Tetrahedron: Asymmetry 2003, 14: 2619

24c

Aldrich Handbook of Fine Chemicals and Laboratory Equipments, India 2003-2004; 336

24d

Aldrich Advancing Science, India 2005-2006; 514

24e

Donboo Amino Acid Co. Ltd., http://www.donboo.com/english/detail.asp?id = 221.

25 Lebel H. Leogane O. Org. Lett. 2005, 7: 4107

26a Garrett RL. In Designing Safer Chemicals: American Chemical Society Symposium Series 640 Garrett RL. De Vito SC. American Chemical Society; Washington DC: 1996. Chap. 1.

26b Cave GWV. Raston CL. Scott JL. Chem. Commun. 2001, 2159

27 Tundo P. Anastas P. Black DS. Breen J. Collins T. Memoli S. Miyamoto J. Polyakoff M. Tumas W. Pure Appl. Chem. 2000, 72: 1207