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

1.3-环丁硫烯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(A)的合成及反应。首次合成了化合物a，在Pd(PPh_3)_4存在下与卤代乙烯偶联得到2-乙烯-3-环丁二烯，再经脱磺酰化得到高立体选择性的共轭三烯。(2)4-亚甲基-2-环丁二烯的合成、反应及其在合成树皮甲虫聚集信息素(&lt；+--)-Ipsenol中的应用。(3)3-羟甲基-3-环丁烯在2-位区域选择性烷基化得到N-(乙酰氧甲基)-3-(t-butyldiphenylsiloxymethyl)-3-sulfolene-2-propamide，，再与N-(乙酰氧甲基)-3-…发生Diels-Alder杂化反应，得到具有理想官能度的吲哚里西丁环更多类型的维生素D采用3-环丁硫烯反应作为关键步骤。合成了1，3，4，7-四氢苯并[c]噻吩基-2，2-二氧化物，再与环己烷缩合，再经脱磺、脱羟基得到维生素D等共轭三烯，为维生素D2的合成提供了一种新的收敛方法。4，6-二氢并[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)在各种条件下，b与典型的亲双烯化合物(3当量)的Diels-Alder反应。化合物b在不同条件下与乙酰二甲酸二甲酯、富马酸二甲酯、顺丁烯二酸二甲酯、顺丁烯二酸酐、N-苯基马来酰亚胺和1，4-萘醌反应，得到4种环加成产物：A类(双亚甲基环合成呋喃)、B类(双环加合)、C类(环合成环丁烯)和D类(环合成呋喃)。反应的类型取决于亲双烯化合物的种类和反应条件(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构件。(2)含共轭三烯的活性维生素D A环的构建。化合物b与环己烷缩醛进行羟烷基化得到GIBE-Aldol产物，再与甲基乙烯基酮进行Diels-Alder环加成得到A类化合物2-(1)。较少

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