TY - JOUR
T1 - Rhodium-catalyzed arylthiolation reaction of nitroalkanes, diethyl malonate, and 1,2-diphenylethanone with diaryl disulfides
T2 - Control of disfavored equilibrium reaction
AU - Arisawa, Mieko
AU - Nihei, Yuri
AU - Yamaguchi, Masahiko
N1 - Funding Information:
This work was supported by Grant-in-Aid for Scientific Research (No. 21229001) from JSPS, and the GCOE program. M. A. expresses her thanks for financial support from the Grant-in-Aid for Scientific Research from MEXT (No. 22689001), Japan Science Technology Agency, and also to the Asahi Glass Foundation.
PY - 2012/10/24
Y1 - 2012/10/24
N2 - In the presence of catalytic amounts of RhH(PPh 3) 4 and 1,2-bis(diphenylphosphino)ethane (dppe), 1-nitroalkanes reacted with a diaryl disulfide giving 1-arylthio-1-nitroalkanes in air. The equilibrium to form thermodynamically disfavored products was shifted by the rhodium-catalyzed oxidation of thiols to disulfides and water. The thiolation reaction of cyclic nitroalkanes proceeded in high yields provided that suitable diaryl disulfides were employed depending on the substrate: di(p-chlorophenyl) disulfide was used for the thiolation reaction of 1-nitroalkanes, 1-nitrocyclopentane and 1-nitrocycloheptane with acidic α-protons (pK a 16 and 17); di(p-methoxyphenyl) disulfide for 1-nitrocyclobutane and 1-nitrocyclohexane with less acidic α-protons (pK a ca. 18). Related reactivities were observed in the thiolation reactions of malonate and 1,2-diphenylethanone.
AB - In the presence of catalytic amounts of RhH(PPh 3) 4 and 1,2-bis(diphenylphosphino)ethane (dppe), 1-nitroalkanes reacted with a diaryl disulfide giving 1-arylthio-1-nitroalkanes in air. The equilibrium to form thermodynamically disfavored products was shifted by the rhodium-catalyzed oxidation of thiols to disulfides and water. The thiolation reaction of cyclic nitroalkanes proceeded in high yields provided that suitable diaryl disulfides were employed depending on the substrate: di(p-chlorophenyl) disulfide was used for the thiolation reaction of 1-nitroalkanes, 1-nitrocyclopentane and 1-nitrocycloheptane with acidic α-protons (pK a 16 and 17); di(p-methoxyphenyl) disulfide for 1-nitrocyclobutane and 1-nitrocyclohexane with less acidic α-protons (pK a ca. 18). Related reactivities were observed in the thiolation reactions of malonate and 1,2-diphenylethanone.
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U2 - 10.1016/j.tetlet.2012.07.132
DO - 10.1016/j.tetlet.2012.07.132
M3 - Article
AN - SCOPUS:84866416551
SN - 0040-4039
VL - 53
SP - 5729
EP - 5732
JO - Tetrahedron Letters
JF - Tetrahedron Letters
IS - 43
ER -