Selective Synthesis of Carbamate Protected Polyamines Using Alkyl Phenyl Carbonates

Michael  Pittelkow; Rasmus  Lewinsky; Jørn Bolstad  Christensen

doi:10.1055/s-2002-34859

PAPER

Selective Synthesis of Carbamate Protected Polyamines Using Alkyl Phenyl Carbonates

Michael Pittelkow, Rasmus Lewinsky, Jørn Bolstad Christensen*
Chemical Laboratory II, The H. C. Ørsted Institute, University of Copenhagen, Universitetsparken 5, 2100 Denmark
Fax: +45(353)20212 ; e-Mail: jbc@kiku.dk;

Abstract

All articles of this category

Abstract

Utilising alkyl phenyl carbonates, an economical, practical and versatile method for selective Boc, Cbz and Alloc protection of polyamines has been developed. This method allows Boc, Cbz and Alloc protection of primary amines in the presence of secondary amines by reaction of the polyamines with the alkyl phenyl carbonates. Also, this method allows mono carbamate protection of simple symmetrical aliphatic α,ω-alkanediamines in high yields with respect to the diamine. Finally, the method allows selective carbamate protection of a primary amine located on a primary carbon in the presence of a primary amine located on a secondary or a tertiary carbon in excellent yields.

Key words

protecting groups - amines - regioselectivity - chemoselectivity - carbonates

Full Text

References

1 Geneste H. Hesse M. Chem. Unserer Zeit 1998, 32: 206

2 Cohen SS. Nature (London) 1978, 274: 209

3 Cohen SS. Introduction to the Polyamines Prentice-Hall; Englewood Cliffs: 1971.

4 Cohen SS. A Guide to the Polyamines Oxford University Press; New York: 1998.

5 de Brabander-van den Berg EMM. Meijer EW. Angew. Chem., Int. Ed. Engl. 1993, 32: 1308

6 Greene TW. Wuts PGM. Protective Groups in Organic Synthesis 3rd ed.: Wiley; New York: 1999.

7 Kuksa V. Buchan R. Lin PKT. Synthesis 2000, 1189

8 Bergeron RJ. Stolowich NJ. Porter CW. Synthesis 1982, 689

9 Zahn H. Falkenburg HR. Liebigs Ann. Chem. 1960, 636: 117

10 Dhanak D. Reese CB. J. Chem. Soc., Perkin Trans 1 1986, 2181

11 Scott JW. Parker D. Parrish DR. Synth. Commun. 1981, 11: 303

12 Sieber P. Iselin B. Helv. Chim. Acta 1968, 51: 622

13 Bartrolí J. Carceller E. Merlos M. Giral M. García Rafanell J. Forn J. J. Med. Chem. 1991, 34: 3328

14 Perich JW. Alewood PF. Johns RB. Aust. J. Chem. 1991, 44: 377

15 Chong JM. Park SB. J. Org. Chem. 1993, 58: 7300

16 Kalbacher H. Voelter W. Angew. Chem., Int. Ed. Engl. 1978, 17: 944

17 Ragnarsson U. Karlsson SM. Sandberg BE. Larsson LE. Org. Synth. 1988, 50: 203

18 Ragnarsson U. Karlsson SM. Sandberg BE. Acta Chim. Scand. 1972, 26: 2550

19 Mikheev VV. Svetlakov NV. Garipov RM. Zh. Org. Khim. 1982, 18: 246

20 Mikheev VV. Svetlakov NV. Garipov RM. Kalmykova ND. Zh. Org. Khim. 1982, 18: 2118

21 Scott JW. Parker D. Org. Prep. Proced. Int. 1980, 12: 242

22 Zahn H. Schmidt F. Makromol. Chem. 1959, 36: 1

23 Larock RC. Lee NH. Tetrahedron Lett. 1991, 32: 6315

24 Matzner M. Kurkjy RP. Cotter RJ. Chem. Rev. 1964, 64: 645

25 Adamczyk M. Fishpaugh JR. Heuser KJ. Org. Prep. Proced. Int. 1998, 30: 339

26 Phanstiel O. Price HL. Wang L. Juusola J. Kline M. Shah SM. J. Org. Chem. 2000, 65: 5590

27 Krapcho AP. Maresch MJ. Lunn J. Synth. Commun. 1993, 23: 2443

28 Krapcho AP. Kuell CS. Synth. Commun. 1990, 20: 2559

29 Atwell GJ. Denny WA. Synthesis 1984, 1032

30 Kovacs HN. Kovacs J. Pisano MA. Shidlovsky BA. J. Med. Chem. 1967, 10: 904

31 Gleim CE. J. Am. Chem. Soc. 1954, 76: 107

32 Hung DT. Nerenberg JB. Schreiber ST. J. Am. Chem. Soc. 1996, 118: 11054

33 Braisted AC, Judice JK, Mcdowell RS, Phelan JC, Starovasnik MA, and Wells JA. inventors; US Patent 6271198. ; CAN Patent 135:122757

34 Hidaka H. inventors; Sone T.; US Patent 4678783. ; CAN Patent 106:32864

35 Maison W. Schlemminger OW. Martens J. Bioorg. Med. Chem. 2000, 8: 1343

36 Grillot AL. Hart DJ. Tetrahedron 1995, 51: 11377