The Woodward-Doering/Rabe-Kindler total synthesis of quinine: setting the record straight

In 1918, Paul Rabe and Karl Kindler reported the three-step conversion of d-quinotoxine into quinine. In 1944 Robert B. Woodward and William von Eggers Doering reported the total synthesis of homomeroquinene and d-quinotoxine from 7-hydroxyisoquinoline. Based on the transformations by Rabe and Kindler, Woodward and Doering asserted the "Total Synthesis of Quinine" (the title of their 1944 and 1945 papers). In 2000 and 2001, Gilbert Stork concluded that the claim by Woodward and Doering is a "myth" because they had synthesized only homomeroquinene and d-quinotoxine; no synthetic quinine had been made in Cambridge. In fact, Rabe and Kindler never published the experimental details of their conversion of d-quinotoxine into quinine. This Review presents the results of a detailed examination of the synthesis of cinchona alkaloids, and previously unpublished material combined with unpublished material and numerous interviews give insight into the lives of the personalities in this nearly 100-year saga.     

金鸡纳生物碱衍生手性双胺配体的合成及其在不对称氢转移反应中的催化作用

 以价廉易得的天然金鸡纳生物碱奎宁和辛可宁为原料,在温和条件下容易地合成了6种手性双胺配体. 考察了它们与过渡金属Ir和Rh形成的配合物在苯乙酮不对称氢转移反应中的催化活性和不对称诱导作用. 结果表明, 9-氨基金鸡纳生物碱配体具有良好的不对称催化活性,而当配体中的氨基被取代后其对映选择性降低. 将9-氨基(9-脱氧)表辛可宁的Ir配合物用于其它芳香酮的不对称氢转移反应时,该配体也显示了很高的催化活性(80%～90%收率)和对映选择性(除对氯苯乙酮ee值为72%外,其余芳香酮ee值均为95%～97%).     

Total Synthesis of (-)-Kaerophyllin,(-)-Hinokinin and (±)-Isohinokinin

Kaerophyllin (1) ,hinokinin (2 )andtheiranalogue isohinokinin (3)belongtothedibenzylbutyrolactone lig nans .Kaerophyllin (1)wasisolatedfromtherootofspot tedcowparsley (ChaerophyllummaculatumWilld .) 1andhinokinin (2 )wasisolatedfromtheheartwoodofLiboce drusformosanaFlorin .2 AccordingtoMacRaeandTow ers ,3afivememberedlactoneringandamethylenedioxylgroupwereimportantstructuralcharacteristicswhichcon tributetotheactivityoflignansasantitumoragents .More over ,anunsaturateddoublebondbetweenC3—…     

Effect of Sensitisers on the Chemiluminescent Reduction of Cerium (IV) by Sulphite

Abstract

The effect of 3-cyclohexylaminopropane sulphonic acid and other compounds which contain cyclohexylgroups on the emission intensity generated during the chemiluminescent oxidation of sulphite by cerium (IV) is investigated. The sensitising action of these compounds remains unclear but their use increases considerably the sensitivity of the determination of sulphite. The use of quinine as a sensitiser by energy transfer is also proposed.     

盐酸奎宁与全氟辛烷磺酸体系的共振光散射光谱研究及其分析应用

研究了盐酸奎宁(Quinine dihydrochloride,简称Quinine)与全氟辛烷磺酸(perfluorooctane sulfonate,简称PFOS)相互作用的共振光散射(resonance light scattering,RLS)光谱,并建立了PFOS的共振光散射分析方法.在pH值为2.87的Britton-Robinson(BR)缓冲溶液中,全氟辛烷磺酸根阴离子与质子化的盐酸奎宁通过静电引力和疏水作用形成2:1的离子缔合物,引起共振光散射强度(IRLS)显著增强,最大散射波长位于283nm处,增强的散射信号强度与PFOS浓度在0.10～50.0μmol/L范围内呈线性关系,据此建立了测定PFOS的散射分析方法,检测限为9.88nmol/L.讨论了体系的最佳反应条件及外来物质的干扰,同时研究了体系的吸收光谱及荧光光谱,并探讨了反应机理.本方法用于水样及人体血清样品中PFOS的测定,RSD≤4.2%.     

Supercritical fluid chromatography as a tool for enantioselective separation; A review

Supercritical fluid chromatography (SFC) has become popular in the field of enantioselective separations. Many works have been reported during the last years. This review covers the period from 2000 till August 2013. The article is divided into three main chapters. The first one comprises a basic introduction to SFC. The authors provide a brief explanation of general principles and possibilities of this method. The advantages and drawbacks are also listed. Next part deals with chiral separation systems available in SFC, namely with the commonly used chiral stationary phases. Properties and interaction possibilities of the chiral separation systems are described. Recent theoretical papers are emphasized in this chapter. The last part of the paper gives an overview of applications of enantioselective SFC in analytical chemistry, in both analytical and preparative scales. Separation systems and conditions are summed up in tables so that they provide a helpful tool for analysts who search for a particular method of analysis.     

味觉电化学传感器的研究 Ⅱ.苦味物质对模拟生物膜膜电位的影响

本文研究了苦味物质盐酸奎宁对胆固醇脂质膜膜电位的影响，发现盐酸奎宁浓度在７５～１２５０μｍｏｌ／Ｌ范围内与膜电位变化值呈线性关系。提出了本体系下苦味物质的定量测定方法，并对该脂质膜对盐酸奎宁的工作机理进行了探讨。     

以四苯硼钠为沉淀剂FI－ICP－AES在线间接测定生物碱奎宁的研究

本文提出了流动注射－电感耦合等离子体原子发射光谱在线间接测定生物碱奎宁的分析方法。该法基于在一定实验条件下，四苯硼钠与奎宁发生沉淀反应，所得沉淀物连续吸附于玻璃微球型微过滤柱上，通过测定参加反应的过量试剂，对奎宁进行在线间接测定。本法测定浓度范围为１２～１６０μｇ／ｍＬ；ＲＳＤ为０．９９％（ｃ＝４０μｇ／ｍＬ，ｎ＝８）；进样速率为４０次／ｈ。结果表明，该法具有简单、快速、准确、试剂和试样消耗量少的优点，可望在临床分析中获得应用。     

过渡元素钼钨钒磷五元杂多配合物的合成、表征以及与奎宁的取代反应

Eight new complexes were synthesized for the first time. The compounds which have the general formula K_xH₂[PM(OH₂)Mo₇W₂V₂O₃₉]·nH₂O(M=Cr³⁺，Mn²⁺，Fe³⁺，Co³⁺，Ni²⁺，Cu²⁺，Zn²⁺， Cd²⁺; x=4 or 5) were de-termined by conductance titration and elemental analysis. The analysis of IR， UV， XRD and ESR show that the products hold the Keggin structure and TG-DTA， IR， XRD at various temperatures and water solubility test also give the evidences that the range of pyrolysis temperature is 300～350℃. The study on the substitutional reaction of coordinated water by optical ligand quinine shows that the S_N2 nucleophilic substitution occures when Ni is con-tained in the compound and S_N1 nucleophilic substitution occures when Cu is contained. These also confirmed that the transitional metals are in the inner sphere of the complexes.