TY - JOUR
T1 - Rhodium-Catalyzed Isomerization and Alkyne Exchange Reactions of 1,4-Dithiins via the 1,2-Ethenedithiolato Rhodium Complex
AU - Arisawa, Mieko
AU - Sawahata, Kyosuke
AU - Ichikawa, Takuya
AU - Yamaguchi, Masahiko
N1 - Funding Information:
This research was supported by the Platform Project for Supporting Drug Discovery and Life Science Research from AMED under Grant JP18am0101100, JSPS KAKENHI Grants 17K19112 and 15H00911, the Tohoku University Center for Gender Equality Promotion (TUMUG), and the Morinomiya-ko Project for Empowering Women in Research.
Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/9/24
Y1 - 2018/9/24
N2 - Rhodium-catalyzed isomerization and alkyne exchange reactions of 1,4-dithiines occurred by cleavage of two C-S bonds. The 2,5- and 2,6-disubstituted 1,4-dithiins underwent isomerization reactions in toluene at 110 °C, providing equilibrium mixtures of isomers. At 150 °C, the reaction of 1,4-dithiins and dimethyl acetylenedicarboxylate gave unsymmetric 2,3-di(methoxycarbonyl)-1,4-dithiins and 2,3-di(methoxycarbonyl)thiophenes, the latter of which were formed by desulfurization of the 1,4-dithiins. A related reaction of the alkyne and a 1,2-dithiete gave a 2,3-di(methoxycarbonyl)thiophene. These reactions are considered to involve 1,2-ethenedithiolato rhodium intermediates.
AB - Rhodium-catalyzed isomerization and alkyne exchange reactions of 1,4-dithiines occurred by cleavage of two C-S bonds. The 2,5- and 2,6-disubstituted 1,4-dithiins underwent isomerization reactions in toluene at 110 °C, providing equilibrium mixtures of isomers. At 150 °C, the reaction of 1,4-dithiins and dimethyl acetylenedicarboxylate gave unsymmetric 2,3-di(methoxycarbonyl)-1,4-dithiins and 2,3-di(methoxycarbonyl)thiophenes, the latter of which were formed by desulfurization of the 1,4-dithiins. A related reaction of the alkyne and a 1,2-dithiete gave a 2,3-di(methoxycarbonyl)thiophene. These reactions are considered to involve 1,2-ethenedithiolato rhodium intermediates.
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U2 - 10.1021/acs.organomet.8b00498
DO - 10.1021/acs.organomet.8b00498
M3 - Article
AN - SCOPUS:85053546129
VL - 37
SP - 3174
EP - 3180
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 18
ER -