Rhodium-catalyzed arylthiolation reaction of nitroalkanes, diethyl malonate, and 1,2-diphenylethanone with diaryl disulfides: Control of disfavored equilibrium reaction

Mieko Arisawa; Yuri Nihei; Masahiko Yamaguchi

doi:10.1016/j.tetlet.2012.07.132

Rhodium-catalyzed arylthiolation reaction of nitroalkanes, diethyl malonate, and 1,2-diphenylethanone with diaryl disulfides: Control of disfavored equilibrium reaction

Mieko Arisawa, Yuri Nihei, Masahiko Yamaguchi

PHA - Molecular Pharmaceutical Science

Research output: Contribution to journal › Article › peer-review

19 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	5729-5732
Number of pages	4
Journal	Tetrahedron Letters
Volume	53
Issue number	43
DOIs	https://doi.org/10.1016/j.tetlet.2012.07.132
Publication status	Published - 2012 Oct 24

Keywords

Arylthiolation
Diaryl disulfide
Disfavored equilibrium
Nitroalkane
Rhodium catalyst

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

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10.1016/j.tetlet.2012.07.132

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title = "Rhodium-catalyzed arylthiolation reaction of nitroalkanes, diethyl malonate, and 1,2-diphenylethanone with diaryl disulfides: Control of disfavored equilibrium reaction",

abstract = "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.",

keywords = "Arylthiolation, Diaryl disulfide, Disfavored equilibrium, Nitroalkane, Rhodium catalyst",

author = "Mieko Arisawa and Yuri Nihei and Masahiko Yamaguchi",

note = "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. ",

year = "2012",

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doi = "10.1016/j.tetlet.2012.07.132",

language = "English",

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pages = "5729--5732",

journal = "Tetrahedron Letters",

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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.

KW - Arylthiolation

KW - Diaryl disulfide

KW - Disfavored equilibrium

KW - Nitroalkane

KW - Rhodium catalyst

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JO - Tetrahedron Letters

JF - Tetrahedron Letters

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ER -

Rhodium-catalyzed arylthiolation reaction of nitroalkanes, diethyl malonate, and 1,2-diphenylethanone with diaryl disulfides: Control of disfavored equilibrium reaction

Abstract

Keywords

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