1-(tert-Butylthio)-1,2-hydrazinedicarboxylic Acid Derivatives. New Reagents for the Introduction of theS-tert-Butylthio Group into Cysteine and Cysteine Derivatives

Abstract

The sterically hindered terf-butyl thiol reacts smoothly with azodicarboxylic acid derivatives only upon addition of catalytic amounts of sodium alcoholate, yielding crystalline and analytically well characterized 1 -(tertbutylthio)-l,2-hydrazinedicarboxylic acid derivatives. These sulfur-activated reagents were found to be stable on storage and well suited as terr-butylthio carriers for the introduction of this thiol-protecting group on cysteine, cysteine derivatives and cysteine peptides;the related compounds are obtained in high yields.l-(tert-Butylthio)-l,2-hydrazindicarbonsäure-Derivate > neue Reagenzien zur Einfuhrung der S-tert-Bu tylth io-Schutzgrupp e Zusammenfassung: ,,Sterisch gehindertes" tertButyl-thiol und Azodicarbonsäure-Derivate lassen sich nur unter katalytischer Einwirkung von Natriumalkoholat in die entsprechenden l -(ferf-Butylthio)-l ,2-hydrazindicarbonsäure-Derivate in hoher Ausbeute umsetzen. Diese TV-Sulfenylhydrazide eignen sich vortrefflich als Alkylthio-Donatoren zur Herstellung von S-te/t-Butylthio-Cystein, -Cystein-Derivaten und -Peptiden aus den Thiol-Verbindüngen. Die Umsetzung verläuft unter milden Bedingungen rasch und mit ausgezeichneten Ergebnissen. Die bei dem bisherigen Verfahren, d.i. die Öffnung von symmetrischen Disulfiden mit tert-Butylthiol im großen Überschuß, auftretende enorme Geruchsbelästigung kommt fast vollständig zum Fortfall.

Luminescent Homo- and Heteropolynuclear Platinum(II) Chalcogenido Aggregates Based on [Pt2E2(P^N)4] Units (E=S, Se)

“…For the forthcoming alkylation of the lactam amide, the corresponding electrophile was needed. To this end, thioester 55 , which was accessible following a literature procedure,33 was treated with sodium methylate, and subsequently the free thiol group was protected as a tert ‐butyl disulfide using the methodology of Wünsch et al (Scheme ) 34. The methoxy tetrahydropyran group in 57 was cleaved and the resulting alcohol was then transformed into the desired mesylate 58 .…”

Synthesis and Evaluation of Acyl Protein Thioesterase 1 (APT1) Inhibitors

“…To this end, thioest-er 55, which was accessible following a literature procedure, [33] was treated with sodium methylate, and subsequently the free thiol group was protected as a tert-butyl disulfide using the methodology of Wünsch et al (Scheme 10). [34] The methoxy tetrahydropyran group in 57 was cleaved and the resulting alcohol was then transformed into the desired mesylate 58.…”

Synthesis of sulfur-containing glycerophospholipids

“…Using a mixed disulfide protocol, Moroder and co-workers [119,120] prepared (±)-1,2-di-O-acyl-3-thioglycerols (97), which may also be used to synthesize thiophospholipids via scheme 30. The mixed t-butyl disulfide functionality was introduced to thioglycerol, using 1-(tbutylthiohydrazine)-1,2-dicarboxmorpholide (BHDM) [119,120] as an electrophilic source of the t-butylthio group.…”

“…The mixed t-butyl disulfide functionality was introduced to thioglycerol, using 1-(tbutylthiohydrazine)-1,2-dicarboxmorpholide (BHDM) [119,120] as an electrophilic source of the t-butylthio group. After esterification of the two hydroxy groups of 103 with fatty acids, disulfide 104 was reduced using Bu 3 P, releasing thiol 97.…”