Glycopeptide and glycoprotein synthesis involving unprotected carbohydrate building blocks.

This review summarizes the chemical and chemoenzymatic synthesis of glycopeptides and glycoproteins using unprotected carbohydrates as key intermediates. The synthetic methods covered herein include the convergent synthesis of glycopeptides by chemoselective ligation of peptides and free glycans, solution- and solid-phase synthesis of glycopeptides by sequential peptide elongation with unprotected glycosyl amino acids or short glycopeptides as building blocks, and the synthesis of glycopeptides by enzymatic and/or chemical elongation of the free glycans. The use of unprotected carbohydrates in these syntheses can circumvent the final-stage carbohydrate deprotection, lead to highly convergent synthetic designs, and more significantly, take advantage of the commercially available free glycans isolated from nature, which could considerably facilitate the synthesis of complex glycopeptides and glycoproteins. (c) 2005 Wiley Periodicals, Inc.