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In addition to previously described nonapeptides consisting of i, i+3 cystine linkages, the reaction has now been extended to systems consisting of shorter (i, i+2) and longer (i, i+4) disulfide bridges. The desulfurization reaction is also compatible with disulfide bridges formed through homocysteines and penicillamines, yielding unusual amino acids such as cystathionine and \u03b2,\u03b2\u2010dimethyl lanthionine (referred to as \u201cpenthionine\u201d) in a peptide chain, respectively. Systematic study of this transformation has provided several new insights into its mechanism. We have observed formation of dehydroalanine and dehydrovaline residues resulting from i, i+2\u2010bridged cysteines and i, i+3\u2010bridged cysteine\/penicillamine peptides, respectively, thereby supporting a \u03b2\u2010elimination\/Michael\u2010addition mechanism for this transformation. Amino acid analysis and NMR data from total correlation spectroscopy (TOCSY) and <jats:sup>1<\/jats:sup>H\u2010<jats:sup>13<\/jats:sup>C heteronuclear single quantum correlation (HSQC) experiments show three diastereomeric lanthionine\u2010bridged peptides in the product mixture. But in the case of desulfurization of a cysteine\/homocysteine containing disulfide\u2010bridged peptide, Michael addition appears to be stereoselective, yielding a single stereoisomer of cystathionine within the peptide. According to molecular modeling and CD spectroscopy, constrained peptides such as those containing penicillamine are less likely to undergo facile desulfurization. Flexibility of the torsional angles (C<jats:sup>\u03b1<\/jats:sup>H\u2014C<jats:sup>\u03b1<\/jats:sup>\u2014C<jats:sup>\u03b2<\/jats:sup>\u2014S) corresponding to the cysteine residues and temperature appear to be contributing factors determining the extent of desulfurization. \u00a9 2003 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 71: 534\u2013551,  2003<\/jats:p>","DOI":"10.1002\/bip.10532","type":"journal-article","created":{"date-parts":[[2003,11,20]],"date-time":"2003-11-20T18:14:33Z","timestamp":1069352073000},"page":"534-551","source":"Crossref","is-referenced-by-count":60,"title":["Understanding base\u2010assisted desulfurization using a variety of disulfide\u2010bridged peptides"],"prefix":"10.1002","volume":"71","author":[{"given":"Amit K.","family":"Galande","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"John O.","family":"Trent","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Arno F.","family":"Spatola","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2004,1,12]]},"reference":[{"key":"e_1_2_4_2_2","series-title":"The Chemistry of Organic Sulfur Compounds","first-page":"337","author":"Danehy J. 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