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Synthesis 2008(3): 438-444
DOI: 10.1055/s-2008-1032029
DOI: 10.1055/s-2008-1032029
PAPER
© Georg Thieme Verlag Stuttgart · New York
Carbamoyl Azides of α-N-Protected Amino Acids: A Fast and Simple One-Pot Synthesis
Further Information
Received
10 October 2007
Publication Date:
10 January 2008 (online)
Publication History
Publication Date:
10 January 2008 (online)
Abstract
A fast and simple one-pot synthesis of carbamoyl azides of α-N-protected amino acids is reported. The procedure involves the reaction between sodium azide and the mixed anhydride obtained from an α-N-protected amino acid and isobutyl chloroformate, in the presence of KH2PO4. The reaction rate was influenced by the nature of both the α-N-protection and the amino acid side chain. Surprisingly, tert-butyloxycarbonyl (α-N-Boc) and benzyloxycarbonyl (α-N-Cbz) protected proline afforded the corresponding isocyanates instead of the expected carbamoyl azides.
Key words
α-N-protected amino acids - sodium azide - carbamoyl azide - mixed anhydride - Curtius rearrangement
-
1a
Lieber E.Minnis RL.Rao CNR. Chem. Rev. 1965, 65: 377 -
1b
Lwowski W. In The Chemistry of the Azido GroupPatai S. Interscience; New York: 1971. p.520-527 -
2a
Wood J, andBull MJ. inventors; DE 2310287. ; Chem. Abstr. 1973, 79, 146504 -
2b
Klich M.Teutsch G. Tetrahedron 1986, 42: 2677 -
2c
Deroose FD.De Clercq PJ. Tetrahedron Lett. 1993, 34: 4365 -
2d
Del Signore G.Fioravanti S.Lellacani L.Tardella PA. Tetrahedron 2001, 57: 4623 - 3a . inventors; British Patent 1152940. ; Chem. Abstr. 1969, 71, 80994
-
3b
Swett LR,Ratajczyk JD, andDarby TD. inventors; US Patent 3424844. ; Chem. Abstr. 1969, 71, 12793 -
3c
Eisenbrand G. inventors; German Patent 2623420. ; Chem. Abstr. 1978, 88, 37285 -
3d
Lam H.-YP.Begleiter A.Goldenberg GJ. J. Med. Chem. 1979, 22: 200 -
3e
Baracu EG,Matei I,Niculescu C, andTeodorescu S. inventors; RO 75828B. ; Chem. Abstr. 1983, 99, 121884 -
3f
Tang W.Schmid J.Fiebig HH.Eisenbrand G. J. Cancer Res. Clin. Oncol. 1986, 111: 25 -
3g
Parameswaran KN.Shi GY.Klotz IM. J. Med. Chem. 1987, 30: 936 -
4a
Suzuki S. inventors; US Patent 3526644. ; Chem. Abstr. 1970, 73, 99592 -
4b
Suzuki S. inventors; US Patent 3547843. ; Chem. Abstr. 1971, 74, 54676 -
5a
Henecka H.Kurtz P. In Methoden der Organischen Chemie (Houben-Weyl) Vol. 8: Georg Thieme Verlag; Stuttgart: 1952. p.684 -
5b
Eardegger E.Meier A.Stoos A. Helv. Chim. Acta 1969, 52: 2555 -
5c
Meier A.Stoos F.Martin D.Buyuk G.Hardegger E. Helv. Chim. Acta 1974, 57: 2622 -
5d
Lwowski W.de Mauriac RA.Thompson M. J. Org. Chem. 1975, 40: 2608 -
5e
Gumaste VK.Deshmukh ARAS. Tetrahedron Lett. 2004, 45: 6571 -
6a
Larson HO.Ooi T.-C.Luke WKH.Ebisu K. J. Org. Chem. 1969, 34: 525 -
6b
Lenoir D.Glaser R.Mison P.Rague Scheleyer P. J. Org. Chem. 1971, 36: 1821 -
7a
Oliveri-Mandala E.Noto F. Gazz. Chim. Ital. 1913, 43: 514 -
7b
Oliveri-Mandala E. Gazz. Chim. Ital. 1914, 44: 662 -
7c
Brugman FW.Arens JF. Recl. Trav. Chim. Pays-Bas 1955, 74: 209 -
7d
Maffei S.Bettinetti GF. Ann. Chim. (Rome) 1959, 49: 1801 -
7e
Neidlein R. Angew. Chem. 1966, 78: 333 -
7f
Neidlein R. Arch. Pharm. 1966, 299: 1003 -
7g
Neidlein R.Bottler R. Chem. Ber. 1967, 100: 698 -
7h
Saikachi H.Takai K. Yakugaku Zasshi 1969, 89: 34 ; Chem. Abstr. 1969, 70, 96507 -
7i
Neidlein R.Krull H. Arch. Pharm. 1971, 304: 749 -
7j
Eisenbrand G. inventors; DE 2659862. ; Chem. Abstr. 1978, 88, 190126 -
7k
Quast H.Bieber L. Chem. Ber. 1981, 114: 216 -
7l
Eisenbrand G. inventors; AU Patent 531375. ; Chem. Abstr. 1984, 100, 120503 -
7m
Baracu I.Tarnauceanu E.Dobre V.Niculescu-Duvaz I. Rev. Roum. Chim. 1985, 30: 317 ; Chem. Abstr. 1985, 103, 134470 - 8
Suzuki H.Nakaya C.Matano Y. J. Chem. Res., Synop. 1992, 34 -
9a
Reddy PS.Yadagiri P.Lumin S.Shin D.-S.Falck JR. Synth. Commun. 1988, 18: 545 -
9b
Marinescu L.Thinggaard J.Thomsen IB.Bols M. J. Org. Chem. 2003, 68: 9453 -
9c
Marinescu LG.Pedersen CM.Bols M. Tetrahedron 2005, 61: 123 -
9d
Pedersen CM.Marinescu LG.Bols M. Org. Biomol. Chem. 2005, 3: 816 -
10a
Ninomiya K.Shioiri T.Yamada S. Tetrahedron 1974, 30: 2151 -
10b
Affandi H.Bayquen AV.Read RW. Tetrahedron Lett. 1994, 35: 2729 -
10c
Froyen P. Synth. Commun. 1996, 26: 4549 -
10d
Gomez-Sanchez E.Marco-Contelles J. Tetrahedron 2005, 61: 1207 -
11a
Vasanthakumar G.-R.Ananda K.Babu VVS. Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem. 2002, 41: 1733 -
11b
Patil BP.Vasanthakumar G.-R.Babu VVS. J. Org. Chem. 2003, 68: 7274 - 12
Anand A.Roy AD.Chakrabarty R.Saxena AK.Roy R. Tetrahedron 2007, 63: 5236 -
13a
Chen FMF.Benoiton NL. Can. J. Chem. 1987, 65: 1224 -
13b
Vogel A. In Vogel’s Textbook of Practical Organic Chemistry 5th ed.: Longman Scietific & Technical; New York: 1989. p.762 and 786