A New Synthesis of Polyquinanes Utilizing alpha-Ketovinylphosphonates

该项目由以下三个主题组成。(1)功能化类环戊烷的简便合成利用我们新开发的1-（环己-1-烯基羰基）乙烯基膦酸酯1成功地实现了环戊烷环化合物的合成。用刘易斯酸或多磷酸处理1得到2-磷酰基环戊烯酮成环化合物，产率为25-71%。溴化（1，3-二氧戊环-2-基）乙基镁与1的Michael加成，然后酸水解和分子内Wittig-Horner反应得到二乙烯基酮2（51-70%）。Nazarov环化反应得到环戊烷环化合物3。(2)膦酸酯碳负离子的芳基化反应及α-芳基甲基膦酸酯的合成应用在DMF中，Cu（I）催化下，膦酸酯碳负离子与芳基碘反应，高产率地合成了α-芳基甲基膦酸酯。以α-（邻甲酰基苯基）甲基膦酸酯、多聚甲醛、肟或肼为原料合成了功能化二氢异喹啉N-氧化物和N-苯基（或烷基）亚胺。1，3-偶极分子与亲偶极分子的1，3-偶极环加成反应得到环加成物。(3)乙烯基膦酸酯的分子内烯反应合成环状萜类化合物以香茅醛或2，6-二甲基-5-庚烯醛为原料，与膦酰基乙酸三乙酯进行Lewis酸促进的分子内烯反应，立体选择性地以较高的产率合成了含膦酰基的环状萜类化合物。萜类化合物与多聚甲醛的Wittig反应，然后分子内烯反应以良好至中等的产率提供双环萜类化合物。

This project is composed of three subjects as mentioned below. (1) Convenient Synthesis of Functionalized CyclopentanoidsA new approach to cyclopentane annulated compounds was successfully achieved by using 1-(cyclopent-1-enylcarbonyl)vinylphosphonates 1, which we newly developed. Treatment of 1 with Lewis acids or polyphosphoric acid led to 2-phosphorylcyclopentenone annulated compounds in 25-71% yields. The Michael addition of (1,3-dioxolan-2-yl)ethylmagnesium bromide to 1, followed by acidic hydrolysis and the intramolecular Wittig-Horner reaction gave divinyl ketones 2 (51-70%). Nazarov cyclization of 2 produced cyclopentane annulated compounds 3 in good yields. (2) Arylation of Phosphonate Carbanions and Synthetic Application of alpha-ArylmethylphosphonatesCopper(I)-catalyzed reaction of phosphonate carbanions with aryliodides in DMF gave alpha-arylated phosphonates in good yields. Functionalized dihydroisoquinoline N-oxides and N-phenyl(or alkyl) imines were synthesized from alpha-(o-formylphenyl)methyl-phosphonates prepared, paraformaldehyde, and oxime or hydrazines. 1,3-Dipolar cycloaddition of the 1,3-dipoles to dipolarophiles gave the cycloadducts. (3) Synthesis of Cyclic Terpenoids via Intramolecular Ene Reaction of VinylphosphonatesLewis acid promoted intramolecular ene reaction of the vinylphosphonates, prepared from citronellal or 2,6-dimethyl-5-heptenal and triethyl phosphonoacetate, gave stereoselectively cyclic terpenoids bearing the phosphono group in good yields. The wittig reaction of the terpenoids with paraformaldehyde, followed by intramolecular ene reaction provided the bicyclic terpenoids in good to moderate yields.