New Synthesis of gem-Bis(phosphono)ethylenes and their Applications

Susumu Inoue; Tatsuo Okauchi; Toru Minami

doi:10.1055/s-2003-41002

PAPER

New Synthesis of gem-Bis(phosphono)ethylenes and their Applications

Susumu Inoue, Tatsuo Okauchi, Toru Minami*
Department of Applied Chemistry, Kyushu Institute of Technology, Sensui-cho,Tobata, Kitakyushu 804-8550, Japan
Fax: +81(93)8843300; e-Mail: minami@che.kyutech.ac.jp;

Abstract

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Abstract

Palladium-catalyzed cross-coupling reaction of α-phosphonovinyl nonafluorobutanesulfonates (nonaflates) 1 with dialkyl phosphites gave versatile intermediate reagents, gem-bis(phosphono)ethylenes 2a-d in 35-93% yields. The reaction of bis(diethylphosphono)ethylene (2a) with tribromomethyllithium to give the Michael adduct 3 was followed by treatment with potassium hydride to form 1,1-dibromo-2,2-bis(phosphono)cyclopropane 4 in 68% yield. The reaction of 2a with [N-(p-toluenesulfonyl)- or N-(methanesulfonyl)imino]phenyliodinane produced the corresponding 1-sulfonyl-2,2-bis(phosphono)aziridines 5a,b in 54-75% yields. Treatment of 2a with sodium or potassium imidazole and a halogenating agent led to [1-halo-2-(1-imidazolyl)ethyl]-1,1-bisphosphonates 7a,b (halogen = Cl, F) in 73-47% yields. Similar reaction using 3-lithiopyridine and a halogenating agent afforded [1-halo-2-(3-pyridyl)ethyl]-1,1-bisphosphonates 8a,b in 83-85% yields.

Key words

palladium-catalyzed cross-coupling reaction - bis(phosphono)ethylene - Michael addition - phosphonic acid - heterocycles

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