- Ring-opening of aziridine-2-carboxamides with carbohydrate C1-O-nucleophiles. Stereoselective preparation of α- and β-O-glycosyl serine conjugates
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The stereoselective formation of the α-GalNAc-Ser linkage via the ring opening of aziridine-2-carboxamides with pyranose C1-O-nucleophiles is described. The process is tolerant to the native C2-NHAc group, can be modulated to provide either the α- or β-glycoside through judicious choice of solvent and metal counterion, and is amenable to other classes of O-glycosyl-Ser constructs such as the β-GlcNAc-Ser and α-Man-Ser linkages. This coupling reaction also led to the development of the o-allylbenzyl (ABn) moiety as a new C-terminus carboxyl protective group, which allows for the use of novel methods for N- and C-terminus extension of amino acids following carbohydrate conjugation. Copyright
- Ryan, Daniel A.,Gin, David Y.
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supporting information; experimental part
p. 15228 - 15229
(2009/03/12)
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- Conjugation of selenols with aziridine-2-carboxylic acid-containing peptides
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The addition of PhSeH to aziridine-2-carboxylic acid containing peptides is described, thus expanding the scope of nucleophiles for the opening of this class of electrophilic peptide substrates. The process offers a new strategy for the generation of usef
- Ide, Nathan D.,Galoni?, Danica P.,Van Der Donk, Wilfred A.,Gin, David Y.
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p. 2011 - 2014
(2007/10/03)
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- Aziridine-2-carboxylic acid-containing peptides: Application to solution- and solid-phase convergent site-selective peptide modification
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The development of a method for site- and stereoselective peptide modification using aziridine-2-carboxylic acid-containing peptides is described. A solid-phase peptide synthesis methodology that allows for the rapid generation of peptides incorporating the aziridine residue has been developed. The unique electrophilic nature of this nonproteinogenic amino acid allows for site-selective conjugation with various thiol nucleophiles, such as anomeric carbohydrate thiols, farnesyl thiol, and biochemical tags, both in solution and on solid support. This strategy, combined with native chemical ligation, provides convergent and rapid access to complex thioglycoconjugates.
- Galonic, Danica P.,Ide, Nathan D.,Van Der Donk, Wilfred A.,Gin, David Y.
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p. 7359 - 7369
(2007/10/03)
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- Site-selective conjugation of thiols with aziridine-2-carboxylic acid-containing peptides
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The synthesis and convergent site-selective conjugation of aziridine-2-carboxylic acid-containing peptides with thiols, both in solution and on solid support, are described. The synthesis and use of FmocAzyOH in this capacity demonstrate both the efficient incorporation and tolerance of the Azy moiety in multistep Fmoc solid-phase peptide synthesis (SPPS), as well as the competence of solution and on-bead ligation through a highly regioselective base-promoted aziridine ring-opening process. Copyright
- Galonic, Danica P.,Van Der Donk, Wilfred A.,Gin, David Y.
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p. 12712 - 12713
(2007/10/03)
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