Abstract
α-Azido carboxylic acids have recently emerged as versatile N- protected equivalents for α-amino acids, especially valuable when the sterically hindered
Cα -dialkylated α-amino acids have to be incorporated. Unsymmetrically substituted Cα -dialkylated α-azido carboxylic acids can be obtained in enantiomerically pure form
by enzymatic resolution of α-azido carboxamides. A l -amidase from Ochrobactrum anthropi NCIMB 40321 accepts 2-azido-2,4-dimethylpentanamide as the substrate and provides
both the corresponding S -configured α-azido carboxylic acid and the R -configured α-azido carboxamide in excellent enantiomeric purity. The former is a
valuable synthetic precursor of α-methylleucine [(α-Me)Leu] in peptide synthesis,
as demonstrated by the successful synthesis of a (α-Me)Leu containing efrapeptin C
analogue.
Key words
azides - bioorganic chemistry - enantiomeric resolution - enzymes - peptides
References <A NAME="RT09704SS-1">1 </A>
Present address: Università di Padova, Dipartimento di Scienze Chimiche, 35131 Padova,
Italy.
<A NAME="RT09704SS-2">2 </A>
Lundquist JT.
Pelletier JC.
Org. Lett.
2001,
3:
781
<A NAME="RT09704SS-3">3 </A>
DalPozzo A.
Ni M.
Muzi L.
Caporale A.
de Castiglione R.
Kaptein B.
Broxterman QB.
Formaggio F.
J. Org. Chem.
2002,
67:
6372
4a </A>
Meldal M.
Juliano MA.
Jansson AM.
Tetrahedron Lett.
1997,
38:
2531
4b </A>
Tornøe CW.
Davis P.
Porreca F.
Meldal M.
J. Pept. Sci.
2000,
6:
549
<A NAME="RT09704SS-5">5 </A>
Jost M.
Greie J.-C.
Stemmer N.
Wilking SD.
Altendorf K.
Sewald N.
Angew. Chem. Int. Ed.
2002,
41:
4267 ; Angew. Chem. 2002 , 114 , 4438
<A NAME="RT09704SS-6">6 </A>
Abrahams JP.
Buchanan SK.
van Raau MJ.
Fearnley IM.
Leslie AGW.
Walker JE.
Proc. Natl. Acad. Sci. U.S.A.
1996,
93:
9420
7a </A>
Gupta S.
Krasnoff SB.
Roberts DW.
Renwick JAA.
Brinen LS.
Clardy J.
J. Am. Chem. Soc.
1991,
113:
707
7b </A>
Gupta S.
Krasnoff SB.
Roberts DW.
Renwick JAA.
Brinen LS.
Clardy J.
J. Org. Chem.
1992,
57:
2306
7c </A>
Matha V.
Weiser J.
Olejnicek J.
Folia Parasitol.
1988,
35:
379
7d </A>
Bandani AR.
Khambay BPS.
Faull JL.
Newton RM.
Deadman M.
Butt TM.
Mycol. Res.
2000,
104:
537
<A NAME="RT09704SS-8">8 </A>
Papathanassiu AE. inventors; (Ergon Pharmaceuticals LLC) U. S. Patent, 6528489.
<A NAME="RT09704SS-9">9 </A>
Nagaraj G.
Uma MV.
Shivayogi MS.
Balaram H.
Antimicrob. Agents Chemother.
2001,
45:
145
<A NAME="RT09704SS-10">10 </A>
Weigelt S.
Sewald N.
Synlett
2004,
726
<A NAME="RT09704SS-11">11 </A>
Sonke T.
Kaptein B.
Boesten WHJ.
Broxterman QB.
Schoemaker HE.
Hans E.
Kamphuis J.
Formaggio F.
Toniolo C.
Rutjes F. In
Stereoselective Biocatalysis
Patel RN.
Marcel Dekker;
New York:
2000.
p.23
<A NAME="RT09704SS-12">12 </A>
Tornøe CW.
Sonke T.
Maes I.
Schoemaker HE.
Meldal M.
Tetrahedron: Asymmetry
2000,
11:
1239
<A NAME="RT09704SS-13">13 </A>
Arnold RT.
Kulenovic ST.
J. Org. Chem.
1978,
43:
3687
14a </A>
Falb E.
Yechezkel T.
Salitra Y.
Gilon C.
J. Pept. Res.
1999,
53:
507
14b </A>
Thern B.
Rudolph J.
Jung G.
Tetrahedron Lett.
2002,
43:
5013
14c </A>
Thern B.
Rudolph J.
Jung G.
Angew. Chem. Int. Ed.
2002,
41:
2307 ; Angew. Chem. 2002 , 114 , 2401
14d </A>
Sewald N.
Angew. Chem. Int. Ed.
2002,
41:
4661 ; Angew. Chem. 2002 , 114 , 4855
<A NAME="RT09704SS-15">15 </A>
Kaptein B.
Boesten WHJ.
Broxterman QB.
Peters PHJ.
Schoemaker HE.
Kamphuis J.
Tetrahedron: Asymmetry
1993,
4:
1113
<A NAME="RT09704SS-16">16 </A>
Göttlich R.
Schopfer U.
Stahl M.
Hoffmann RW.
Liebigs Ann./Recl.
1997,
1757
<A NAME="RT09704SS-17">17 </A>
Meyers AI.
Tempel DL.
Nolen RL.
Mihelich ED.
J. Org. Chem.
1974,
39:
2778
<A NAME="RT09704SS-18">18 </A>
Roberts A.
Jaguelin S.
Guinamant JL.
Tetrahedron
1986,
42:
2275
<A NAME="RT09704SS-19">19 </A>
Sonke, T.; Ernste, S.; Tandler, R. F.; Kaptein, B.; Peeters, W. P. H.; van Assema,
F. B. J.; Wubbolts, M. G.; Schoemaker, H. E. An l -Selective Amidase with Extremely Broad Substrate Specificity from Ochrobactrum anthropi NCIMB 40321, submitted.
