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In Pursuit of an Acetylenedithiolate Synthesis
Author(s) -
Seidel Wolfram W.,
Meel Matthias J.,
Schaffrath Markus,
Pape Tania
Publication year - 2007
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200601107
Subject(s) - chemistry , synthon , alkyne , methyllithium , acetylene , bromide , derivative (finance) , medicinal chemistry , protecting group , carbon disulfide , stereochemistry , sulfur , organic chemistry , catalysis , alkyl , financial economics , economics
Acetylene disulfides RSC 2 SR, which are furnished with typical thiol protection groups R, were synthesized, fully characterized, and tested with respect to the aimed cleavage of R. While the alkyne RSC 2 SR with R = C 2 H 4 SiMe 3 is easily accessible, the corresponding disulfide with R = CPh 3 can be prepared only with difficulties, and attempts to use the SiMe 3 group lead to the isolation of a dithiacyclopentene derivative. The molecular structures of Ph 3 CSC 2 SCPh 3 and Ph 3 CSC 2 H, which were investigated by X‐ray diffraction, show a remarkable combination of long and very short carbon–sulfur single bonds. However, removal of the trityl groups by sodium phenolate or methyllithium in THF led to intractable solutions. In contrast, removal of both trimethylsilylethyl groups in Me 3 SiC 2 H 4 SC 2 SC 2 H 4 SiMe 3 with (Bu 4 N)F in THF proceeded smoothly, if benzyl bromide as the trapping agent is present. Hence, the successful transfer of the C 2 S 2 2– synthon in solution was proven by isolation of BnSC 2 SBn.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)