Studies on the reactions of 3-sulfolenes and their application to the Synthesis of ph-siologically active compounds.

1. 3-环丁砜的反应及其在天然产物合成中的应用。(1)2-三丁基锡基-3-环丁烯砜（a）的合成和反应。首次合成了化合物a，并在Pd（PPh 3）4存在下与卤代乙烯偶联得到2-乙烯基-3-环丁砜，再经双酰化反应得到高立体选择性的共轭三烯。(2)4-亚甲基-2-环丁砜的合成、反应及其在<plus-minus>小蠹聚集信息素（±）-伊普森醇合成中的应用。(3)吲哚里西啶生物碱--杜英碱A和B的有效合成。将3-羟甲基-3-亚砜烯在2-位进行区域选择性烷基化，并将所得3-亚砜烯衍生物制备成N-（乙酰氧基甲基）-3-（叔丁基二苯基亚砜基甲基）-3-亚砜烯-2-丙酰胺，将其进行杂Diels-Alder反应，以提供具有所需官能度的中氮茚环用于油豆碱A和B。(4)活性- ...更多信息 以3-环丁烯砜反应为关键步骤合成维生素D。合成了1，3，4，7-四氢苯并[c]噻吩2，2-二氧化物，与环己烷甲醛进行羟醛缩合，然后进行连续的双酚A酰化和脱羟基反应，得到类似于维生素D中的共轭三烯。这基本上为维生素D.2提供了一种新的收敛合成方法。4，6-二氢噻吩并[3，4-c]呋喃5，5-二氧化物（B）的合成、反应及其在天然产物合成中的应用。(1)B与典型的亲二烯体（3当量）在各种条件下的狄尔斯-阿尔德反应。化合物B与乙炔二甲酸二甲酯、富马酸二甲酯、马来酸二甲酯、马来酸酐、N-苯基马来酰亚胺和1，4-萘醌在各种条件下反应，得到四种环加合物; A型（环加合到具有双亚甲基的呋喃）、B型（双环加合物）、C型（单环加合到环丁烯砜）和D型（环加合到呋喃）。反应的类型取决于亲双烯体的种类和反应条件（溶剂、温度、时间和压力）。这些反应表明，B是合成蒽环类抗生素等生物活性化合物的有用结构单元。(2)包括共轭三烯的活性型维生素D的A环的构建。化合物B与环己基甲醛发生羟烷基化反应得到Aldol产物，再与甲基乙烯基酮进行Diels-Alder环加成反应得到A型化合物2-（1）。少

1. Reactions of 3-sulfolenes and their application to the synthesis of natural products. (1) Synthesis and reactions of 2-tributylstannyl-3-sulfolene(a). Compound a was synthesized for the first time and coupled with vinyl halides in the presence of Pd(PPh3)_4 to give 2-vinyl-3-sulfolenes which underwent desulfonylation to afford conjugate trienes highly stereoselectively. (2) Synthesis and reaction of 4-methylene-2-sulfolene and its application to the synthesis of (<plus-minus>)-Ipsenol, the aggregation pheromone of bark beetles. (3) Efficient synthesis of a indolizidine alkaloid, Elaeokanine A and B. 3-Hydroxymethyl-3-sulfolene was alkylated regioselectively at the 2-position and resulting 3-sulfolene derivative was manupulated to give N-(acetyloxymethyl)-3- (t-butyldiphenylsiloxymethyl)-3-sulfolene-2-propamide, which was suniected to hetero- Diels-Alder reaction to provide indolizidine ring having desired functionality for the Elaeokanine A and B. (4) Convergent synthesis of active- … More type vitamin D using 3-sulfolene reaction as a key step. 1,3,4,7-Tetrahydro-benzo[c]thiophene 2,2-dioxide was synthesized and subjected to Aldol condensation with cyclohexanecarbaldehyde followed by successive desulfonylation and dehydroxylation to give the conjugated triene such as that in vitamin D. This provides basically a novel convergent synthetic method for vitamin D.2. Synthesis and reactions of 4,6-dihydrothieno[3,4-c]furan 5,5-dioxide (b) and their application to the synthesis of natural products. (1) Diels-Alder reactions of b with typical dienophiles (3 equivs) under a variety of conditions. Compound b reacted with dimethyl acetylenedicarboxylate, dimethyl fumarate, dimethyl maleate, maleic anhydride, N-phenylmaleimide, and 1,4-naphthoquinone under various conditions to furnish four kinds of cycloadduct; type A (cycloadduct to furan having bismethylene), type B(biscycloadduct), type C(monocycloadduct to sulfolene), and type D(cycloadduct to furan). The type of reaction depends on the kind of dienophile and reaction conditions(solvent, temperature, time, and pressure). These reactions demonstrate that b is a useful building block for synthesizing bioactive compounds such as anthracycline antibiotics. (2) Construction of the ring A of active-type vitamin D including conjugated triene. Compound b was hydroxyalkylated with cyclohexanecarbaldehyde to gibe Aldol product, which undrewent Diels-Alder cycloaddition with methyl vinyl ketone to afford type A compound in 2-(1). Less