(E,E)-3,7-二甲基-2,6-癸二烯-1,10-二醇的高立体选择性合成

1969年Meinwald等[1]从一系列雄性蝴蝶的"hair pencils"中分离得到一组信息素成分,包括一类新颖的开链倍半萜骨架化合物1-3.尽管这些化合物在结构上与香叶醇相似,但利用香叶醇为原料进行合成的报道[2～5]还不多见.本文以香叶醇为原料,报道了化合物3的一条简便、高立体选择性的合成路线.其关键反应步骤是2,3-环氧醇的碘代重排反应和烯丙基烯基醚的克莱森重排反应.     

（E,E）—2,8—二甲基—5—异丙烯基—2,8—癸二烯—1,10—二醇的新合成路线

β—榄香烯(2)是一种重要单环倍半萜化合物,存在于多种精油中,对它的化学性质、结构和生物活性进行了研究,标题化合物(1)是合成(2)的关键中间体,Vig等人曾以(E)—2—甲基—2—庚烯—6—酮酸乙酯的乙二醇缩酮为原料,通过七步反应合成了1。但步骤     

辅酶Q10的重要中间体——(2E,6E)-8-乙酰基-2,6-甲基-2,6-辛二烯-1-醇的合成

在CH2Cl2-H2O-NaCl溶液中,香叶醇的末端烯丙基经电解转变成烯丙基氯化物(2),2与二甲胺反应生成末端烯丙基胺(3),3再用过氧乙酸氧化形成烯丙基二甲基胺氧化物后,通过[2,3]-σ重排,再经锌粉还原得到辅酶Q10的重要中间体——2E,6E)-8-乙酰基-2,6-甲基-2,6-辛二烯-1-醇(7),7的结构经1H NMR和IR表征,且全为末端反式烯丙型醇。     

Synthesis of 1—（2′—Phenyl）cycloproply1—2,3—epoxypropan—1—ol as the Radical Precursor for the Kinetic Study of Oxiranylcarbinyl Radical

We have successfully synthesized 1-(2′-Phenyl)cycloproply1-2,3-epoxypropan-1-ol 3,which will be applied to the kinetics study of oxiranylcarbinyl radical.     

酞菁亚铁／亚碘酰苯催化3—（1‘，3 ’—二氧戊环）—5（10），9（11）—雌甾二烯—17—α—（1—丙炔）—17—β—醇的选择环氧化

目前 ,对酞菁过渡金属配合物的研究已引起人们广泛的重视 .酞菁过渡金属催化烯烃的环氧化反应 ,可以看作是对自然界生物体内许多酶催化氧化反应的模拟[1] .其反应条件温和 ,环氧化产物具有较高的区域选择性和立体选择性 ,可应用于合成特定构型的环氧化物 ,特别是用于合成药物中间体 .用 F3CCOCF3/H2 O2 作环氧化剂对药物中间体 3 -(1′,3′-二氧戊环 ) - 5 (1 0 ) ,9(1 1 ) -雌甾二烯 - 1 7- α- (1 -丙炔基 ) - 1 7-β-醇 (1 )的环氧化反应 ,已有文献报道 [2 ,3] ,5 α、 1 0 α-环氧化物 (2 )与 5 β、 1 0 β-环氧化物(3 )的摩尔比为…     

5，5—二甲基—2—氧代—2—（N，N‘—对苯二胺基—二苄基）—二—1，3，2—氧磷杂环已烷的合成及表征

以新戊二醇、三氯化磷和乙醇为原料制得中间体5,5-二甲基-1,3,2-二氧磷杂环已烷-2-氧（DPDO）,用DPDO与由芳醛和对苯二胺缩合制得的席夫碱SBⅠ-SBⅡ加成,合成了膨胀型阻燃剂5,5-二甲基-2-氧代-2-（N,N‘-对苯二胺基-二苄基）-二-1,3,2-氧磷杂环已烷（DPPOⅠ-DPPOⅡ）,通过元素分析,IR,NMR和MS对其结构进行表征,并对其在醇酸清漆中的应用进行了讨论。     

偕双硅2,3-环氧醇区域及立体选择性环氧开环/卤代反应研究

C³-位偕双硅取代的2,3-环氧醇分别与对甲苯磺酰氯、溴素和单质碘发生C³-位区域及立体选择性环氧开环/卤代反应合成了15个新的C³-位卤代偕双硅基1,2-二醇类产物,收率64%~87%,其结构经¹H NMR, ¹³C NMR和HR-MS（ESI）表征。产物的立体结构经3-［二甲基（苯基）甲硅烷基］-3-碘-3-（三甲基甲硅烷基）丁烷-1,2-二醇(8d)的X-射线单晶衍射确证。     

Highly Stereoselective Synthesis of (E, E)-3,7-Dimethyl-2,6-decadiene-1, 10-diol

Thediol1,aqueenbutterflypheromonewasisolatedfromqueenbutterfly(Danausgillippusbelenice).SynthesesofthiscompoundwerereportedfromtheorthoesterClaisenrearrangement2,therearrangementofallylsiloxylinylether3andtheanionic[2,3]-sigmatropicrearrangementofallylicsulfide4.Inlightoftheirbiologicalinterest,itseemeddesirabletodesignamoreefficientroutetothissubstance.Thus,wewishtoreportashort,stereoselectivesynthesisof1utilizingthe1,3-transformationof2,3-epoxyalcoholandtheClaisenrearrangementofallylvinylet…     

Total Synthesis of (3S, 6S)- ( )-3,7-Dimethyl-3-acetoxy-6-hydroxy-octa-1,7-diene

CompoundI',anovelmonoterpenoid,wasisolatedfromMulisiaspinosa(Compositae).Thestructureofl,determinedbyspectroscopictechniques,correspondedto3,7dimethyl-3-acetoxy-6-hydroxy-cotl,7-diene(thenameof6-hydroxy-7(9)-dehydro-6,7dihydronerylacetateinreferenceIisuncorrect).HowevertheabsoluteconfigurationsatC-3andC-6werenotdetermined.CompoundIwassynthesizedbyphotooxidationoflinalylacetate=,howevertheauthorsobtainedtheisomermixtureof1.Hereinwereportthetotalsynthesisof(3S,6S)-( )-1fromgeraniol2throughsi…     

Syntheses of (4E,6E, 11Z)-4,6,11-hexadecatrienyl acetate and (4E, 6E, 11Z)-4,6,11-hexadecatrienal, female sex pheromones of eri-silkworm, Samia cynthia ricini (Lepidoptera: Saturniidae)

Syntheses of (4E,6E,11Z)-4,6,11-hexadecatrienyl acetate (1) and (4E,6E, 11Z)-4, 6,11-hexadecatrienal (2), female sex pheromones of eri-silkworm,Samia cynthia ricini have been achieved through Claisen ortho ester rearrangement of (6).     

A Highly Stereoselective Synthesis of (E,E)-1,5-Dienes

Several representative 1,5-dienes were synthesized, with a high degree of regioselectivity, by a series of nitrone cycloadditions and subsequent deamination of the adducts.     

Crystal Structure of （E,E）-1,10-Bis-（4-fluoro-phenyl）-3,8-dimethyl-deca-3,7-diene-1,10-dione

1 INTRODUCTION The direct use of metallic samarium as the re-ducing agent in organic transformations has attractedthe attention of many organic chemists[1]. In our inves-tigations on the applications of metallic samarium inorganic synthesis, we have recently found that me-tallic samarium exhibits some extraordinary capa-bilities when DMF instead of traditional THF wasused as the reaction medium[2]. β,γ-Unsaturated car-bonyl moieties, known to exist in natural products,serve as versati…     

Stereoselective total synthesis of (±)-α-vetispirene, (±)-hinesol, and (±)-β-vetivone based on a Claisen rearrangement

The stereoselective total syntheses of (±)-α-vetispirene, (±)-hinesol, and (±)-β-vetivone were accomplished based on a Claisen rearrangement in an alkenyl bicyclic dihydropyran system. The most striking feature of this approach is that the Claisen rearrangement of bicyclic dihydropyran proceeds stereoselectively to provide a multi-functionalized spiro[4.5]decane, which is an efficient precursor for the synthesis of the vetivane sesquiterpenes.     

Synthesis of (R)(E)-3,7-Dimethyl-2-octene-1,8-dioic Acid, a Copulation Released Pheromone Component of Azuki Bean Weevil

IntroductionIn 1 981 ,Tanaka et al.[1] isolated andidentified the copulation released pheromone ofazuki bean weevil,callosobruchus chinensis L,which was a mixture of two major components,onewas1 1 ,1 5 - dimethyl tritriacontane,the other was anew monoterpene dicarboxylic acid,(R) (E) - 3 ,7-dimethyl- 2 - octene- 1 ,8- dioic acid (1 ) ,orcallosobruchusic acid. Since then,severalsyntheses have been reported[2— 4 ] ,the synthesis ofboth the enantiomers of (E) - 3 ,7- dimethyl- 2 -octene- 1 ,8-…