小注:
Reagent for amino group protection as the t-butyl carbamate (t-butoxycarbonyl, Boc derivatives), in high yield under mild conditions, widely used in peptide chemistry[1,2]. Benzyl carbamates(Cbz, Z) may be transformed into Boc in a one pot procedure catalysed by Pd/C[3] . Amides can be protected in the presence of a catalytic quantity of DMAP[4,5]; the amide link of the product undergoes facile alkaline hydrolysis or methanolysis. The nitrogen function of indoles and pyrroles can also be protected under similar conditions[6,7]. 1-Boc indoles may be synthesized from N-Boc 2-alkyl aniline [8]. The Boc group is readily cleaved with acid, most often Trifluoroacetic acid. In the presence of 1 equivalent of DMAP in acetonitrile, arylamines are converted to isocyanates, generally in high yield; the dicarbonate here behaves as a convenient phosgene replacement[9] . The same reagent system has also been applied nitroalkanes for the ambient temperature generation of nitrile oxides which were trapped in situ with dipolarophiles[10] . Feature on uses of this reagent in synthesis was reveiwed[11]. Ref:
- Org.Synthe.Coll., 1990, 7, 70
- Synthesis, 223 (1987): Org.Synthe.Coll., 1998, 9, 124, 300
- Tetrahedron Lett., 1992, 33, 3167
- J. Org.Chem., 1983,48, 2424
- Acta Chem. Scand.B, 1986, 40, 745
- J.Chem.Soc., Chem. Commun., 1984, 1699
- Org.Synth.Coll., 1998, 9, 121
- Synthesis, 1991, 871
- Angew, Chem.Int.Ed., 1995, 34, 2497
- Synthesis, 1997, 309
- Synlett, 2001, 1995
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