The steric structure of multiflorine methylation products

Summary Multiflorine (1) — a minor lupine alkaloid — treated by methyl lithium or methyl magnesium iodide affords 4S-4-hydroxy-4-methyl-2,3-didehydrosparteine (2) and 2S-2-methyl-4-oxosparteine (3), respectively, as the dominating products. Their steric structure, determined by¹H and¹³C NMR techniques, points to stereospecific preferences of these reactions. The observed nucleophilic 1,2- and 1,4-additions indicate that regiospecificity of the action of MeLi or MeMgI on multiflorine is different from that of the so far known similar alkylation of other enamino ketones.

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Die räumliche Struktur von Methylierungsprodukten des Multiflorins

Zusammenfassung Multiflorin (1), ein Lupin-Nebenalkaloid, ergibt bei Umsetzung mit Methyllithium oder Methylmagnesiumiodid 4S-4-Hydroxy-4-methyl-2,3-didehydrospartein (2) und 2S-2-Methyl-4-oxospartein (3) als Hauptprodukte. Ihre NMR-spektroskopisch (¹H und¹³C) aufgeklärte räumliche Struktur weist auf eine Stereoselektivität der erwähnten Reaktionen hin. Die beobachteten nucleophilen 1,2- und 1,4-Additionen zeigen, daß sich die Regiospezifität der Einwirkung von MeLi oder MeMgl auf Multiflorin von jener bis jetzt bekannter Alkylierungen von Enaminoketonen unterscheidet.

     

Alkaloids from Fritillaria Hupehensis

Phytochemical investigation of the bulbs of Fritillaria hupehensis resulted in the isolation and structural elucidation of a new highly conjugated alkaloid of veratramine type identified as 3β,23β-dihydroxy-7,12（14）-dien-5α- veratramin-6-one （1）, together with two known alkaloids, ebeinine （2） and zhebeinine （3）, which were isolated for the first time from F. hupehensis. The structures of alkaloids 1-3 were established by extensive 1D and 2D NMR spectral analyses.     

亚胺参与的Diels-Alder反应及其在生物碱全合成中的应用

在通过Diels-Alder反应建立各种含氮六员环的反应中,亚胺是一个最有用的亲双烯试剂。该法应用简便、并显示出较好的位置选择性和立体选择性。对其在生物碱类合成中的应用也作了综述。     

Concavine, an unusual diterpenic alkaloid produced by the fungus Clitocybe concava

A novel alkaloid with an unprecedented ring system consisting of a dodecahydro-7-oxa-9a-aza-benzo[a]azulene ring (1), has been isolated from cultures of Clitocybe concava (Basidiomycetae). Its structure and relative stereochemistry were elucidated on the basis of spectroscopic data. Concavine presents a weak antibacterial activity.     

A novel synthesis of substituted quinolines using ring-closing metathesis (RCM): its application to the synthesis of key intermediates for anti-malarial agents

A method for synthesizing substituted quinolines using ruthenium-catalyzed ring-closing metathesis as a key step has been developed. Substituted 1,2-dihydroquinolines, 4-silyloxy-1,2-dihydroquinoline and 4-methoxy-1,2-dihydroquinoline, were successfully synthesized in excellent yields via ene-ene metathesis and silyl or alkyl enol ether-ene metathesis, respectively. The synthetic intermediates of the antimalarial agents quinine, chloroquine, and PPMP-quinine hybrid were efficiently synthesized by this methodology.     

Asymmetric synthesis of (+)-1-epiaustraline and attempted synthesis of australine

A diastereoselective synthesis of the pyrrolizidine alkaloid, (+)-1-epiaustraline has been achieved via a diastereoselective syn-dihydroxylation of a pyrrolo[1,2-c]oxazol-3-one precursor that was readily prepared by a RCM reaction. Attempts to extend this methodology to the synthesis of australine were not successful since the final pyrrolidine ring closure to produce the desired pyrrolizidine of the target molecule was not productive.     

含金鸡纳碱的光活性聚合物──Ⅰ．金鸡纳碱／丙烯酰胺共聚物的合成与表征

研究了金鸡纳碱与丙烯酰胺的自由基共聚反应。发现在氯仿／乙醇混合溶剂中采用硫酸奎宁作为金鸡纳碱共聚单体可以合成收率和金鸡纳碱含量均较高的新型水溶性共聚物。对共聚物用元素分析、核磁共振、粘度和旋光度测定等方法进行表征，发现在假定丙烯酰胺链节为非光活性的条件下共聚物中金鸡纳碱链节的比旋光度随聚合配方中金鸡纳碱含量的增加而增加。     

Structures and cytotoxicities of fascaplysin and related alkaloids from two marine phyla—Fascaplysinopsis sponges and Didemnum tunicates

The structural variations and bioactivity properties of the alkaloids in the fascaplysin (1) and the reticulatine (3) families were examined. Four organisms were analyzed consisting of two collections of the sponge Fascaplysinopsis reticulata and two collections of the tunicate Didemnum sp. Reported are the isolation of three new compounds: 3-bromofascaplysin (2), 14-bromoreticulatine (4), and 14-bromoreticulatate (6) along with reticulatate (5) previously known as a semi-synthetic product of 1. Compounds 1 and 5 showed selectivity in a cell based cytotoxicity assay.     

Alkaloids of Nitraria sibirica. Structures of Nitraramidine and Nitraraidine

Two new alkaloids nitraramidine and nitraraidine were isolated from the aerial part of Nitraria sibirica. Their structures were established using spectral data and chemical transformations.     

Role of the C3-substituted derivatives of cinchonidine in the enantioselective hydrogenation of ethyl pyruvate on Pt-alumina catalyst in AcOH

Summary The enantioselective hydrogenation of ethyl pyruvate (EtPy) was studied on Pt-alumina catalysts modified by C3-substituted cinchonidines (NC, A, B, C1, C2in Fig. 1) and for comparison by DHCDand MeO-DHCDin AcOH. The effect of the C3-substituent on the reaction rate and the enantioselectivity were examined. Using the Engelhard 4759 catalyst under mild experimental conditions (room temperature, hydrogen pressure 1 bar) such as DHCDthe (R)-ethyl lactate formed in excess (e.e.max: 79-91%)</o:p>