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Reagent for the introduction of the Boc protecting group.Di-tert-butyl dicarbonate is a reagent used for the introduction of BOC protecting group. It plays an important role in the preparation of 6-acetyl-1,2,3,4-tetrahydropyridine by reacting with 2-piperidone. It serves as a protecting group used in solid phase peptide synthesis.
Reagent for amino group protection as the tert-butyl carbamate (tert-butoxycarbonyl, Boc derivatives), in high yield under mild conditions, widely used in peptide chemistry; see Appendix 6. For practical details, literature references and tabulated results, see: Org. Synth. Coll., 7, 70 (1990). For further examples see: Synthesis, 223 (1987): Org. Synth. Coll., 9, 124, 300 (1998). Benzyl carbamates (Cbz, Z) may be transformed into Boc in a one pot procedure catalyzed by Pd/C: Tetrahedron Lett., 33, 3167 (1992).
Rapid and efficient formation of Boc derivatives of amines, catayzed by Copper(II) tetrafluoroborate hexahydrate, 26127 has been described: Tetrahdron Lett., 47, 1087 (2006).
For Boc protection of phenols, alcohols, thiols etc. under phase-transfer conditions, see: Can. J. Chem., 63, 153 (1985).
Amides can be protected in the presence of a catalytic quantity of DMAP ( 4-(Dimethylamino)pyridine, A13016 ): J. Org. Chem., 48, 2424 (1983); Acta Chem. Scand. B, 40, 745 (1986); 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: J. Chem. Soc., Chem. Commun., 1699 (1984); Org. Synth. Coll., 9, 121 (1998). 1-Boc indoles may be synthesized from N-Boc 2-alkylanilines: Synthesis, 871 (1991).
The Boc group is readily cleaved with acid, most often Trifluoroacetic acid, L06374 .
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: Angew. Chem. Int. Ed., 34, 2497 (1995). The same reagent system has also been applied to nitroalkanes for the ambient temperature generation of nitrile oxides which were trapped in situ with dipolarophiles: Synthesis, 309 (1997). Carboxylic acids can be esterified in the presence of a catalytic amount of DMAP: Synlett, 263 (2004).
Carboxylic acids have also been converted to Boc-protected amines, via a one-pot Curtius rearrangement, using the reagent in the presence of sodium azide, with catalytic amounts of TBAB and zinc triflate: Org. Lett., 7, 4107 (2005).
For a brief feature on uses of the reagent in synthesis, see: Synlett, 1995 (2001).
Hong, X.; Wang, H.; Liu, B.; Xu, B. Ruthenium-catalyzed double-fold C-H tertiary alkoxycarbonylation of arenes using di-tert-butyl dicarbonate. Chem. Commun. 2014, 50 (91), 14129-14132.
Sweis, R. F.; Wang, Z.; Algire, M.; Arrowsmith, C. H.; Brown, P. J.; Chiang, G. G.; Guo, J.; Jakob, C. G.; Kennedy, S.; Li, F.; Maag, D.; Shaw, B.; Soni, N. B.; Vedadi, M.; Pappano, W. N. The Discovery of A-893, A New Cell-Active Benzoxazinone Inhibitor of Lysine Methyltransferase SMYD2. ACS Med. Chem. Lett. 2015, 6 (6), 695-700.
Hazard Statements: H228-H330-H315-H318-H317-H335
Flammable solid. Fatal if inhaled. Causes skin irritation. Causes serious eye damage. May cause an allergic skin reaction. May cause respiratory irritation.
Precautionary Statements: P280-P305+P351+P338-P304+P340-P310a-P302+P352a
Wear protective gloves/protective clothing/eye protection/face protection. IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. IF INHALED: Remove to fresh air and keep at rest in a position comfortable for breathing. Immediately call a POISON CENTER/doctor IF ON SKIN: Wash with plenty of water.