Treatment of lithiated homoallylic phosphonates with dimethyl carbamyl chloride gave 2-amidophosphonate derivatives. A solution of 2-amidophosphonate in dimethoxy ethane DME-$H_2O$(2:1 vol) reacted with 2eq. iodine at room temperature to give α-phosphono-γ-iodoalkyl-γ-butyrolactones in good yield. We did not have to isolate the cis-and trans-isomers of α-phosphono-γ-iodoalkyl-γ-butyrolactones, because the stereoisomers afforded same α-methylene-γ-iodoalkyl-γ-substituted-γ-butyrolactone derivatives by Wadsworth-Emmons reaction. But, we have examined the stereoselectivity of cis-and trans-isomers by $^{13}C$ NMR integrals. Despite,trans-isomers are more stable,the stereoselectivity of is not found, the reason of decreased stereoselectivity is the coodination factor of electon pairs of oxygen with partial cationic nitrogen of amide when iodocyclization is occurred.
The Treatment of diethyl 1-alkynyl phosphonates with an organocuprates was followed by a quench with saturated ammonium chloride solution (E=H).Mostly, organocuprates attact at the 2-position of 1-alkynylphosphonates vicinally. And 2,2-disustituted vinyl phosphonates could be obtained high yields and stereoselectivity controlled very highly. The geminal difuntionalization of vinyl phosphonates were performed by adding 1-alkynyl phosphonates in THF to cuprates in THF at -78℃. Electrophiles were added dropwise and the reactions allowed to warm to r.t. (1h). Except E= PhSeBr, We could obtain 1,2,2-trisustitued vinyl phosphonates high yields and stereoselectivity.
호모알릴포스포네이트의 음이온에 카르바밀크로라이드를 반응시켜 2-아미도호모알릴포스포네이트를 만들고, 이 포스포네이트 유도체를 요오드 고리화 반응을 통해 알파포스포노감마아이오도알킬감마부치로락톤을 만들었다. 이러한 고리화 반응을 통해 얻어진 알파포스포노감마부치로락톤은 처음 만들어진 물질이며, 이 락톤 유도체는 알파메칠렌감마부치로락톤을 합성할 때, 아주 유용한 전구체가 될 수 있다.
1-알카인일포스포네이트는 유기구리화합물과 반응하여 한 용기안에서 높은 위치선택성과 입체선택성을 가진, 같은 탄소에 이중으로 기능화된 바이닐포스포네이트를 쉽고 빠르게 얻을 수 있다. 위치선택성은 포스포네이트에 의한 음이온 안정화효과에 의한 것으로 생각되어 지고, 입체선택성은 유기구리화합물이 탄소-탄소 삼중결합에 같은쪽에서 반응하기 때문이라고 생각된다. 여기서 얻어지는 바이닐포스포네이트는 기존의 방법으로는 쉽게 얻을 수 없는 것들로서, 앞으로 유기합성에 많이 이용될 수 있는 물질들로 기대된다.
