实时直接分析-串联质谱法快速筛查火锅底料、牛肉面汤及调味料中罂粟壳生物碱

建立了采用实时直接分析-串联质谱(DART-MS/MS)对火锅底料、牛肉面汤及调味料中5种非法添加的罂粟壳生物碱进行快速筛查的方法。样品经乙腈提取净化后,在离子化温度为300℃、栅极电压为150 V、进样速率为0.8 m m/s的DART离子源正离子模式条件下进样,以电喷雾离子源正离子多反应监测(MRM)模式进行检测,实现了样品经简单预处理后使用DART-MS/MS进行检测的新方法。该方法简便、快速,能满足大批量非法添加样品的快速筛查分析要求。     

Unprecedented C_(19)-diterpenoid alkaloid glycosides from an aqueous extract of “fu zi”: Neoline 14-O-L-arabinosides with four isomeric L-anabinosyls

Four structurally unprecedented aconitane-type C_(19)-diterpenoid alkaloid glycosides with isomeric arabinosyls, named aconicarmichosides A–D(1–4), were isolated from an aqueous extract of "fu zi", the lateral roots of Aconitum carmichaelii. Their structures were determined as neoline 14-O-a-and 14-O-b-L-arabinopyranosides(1 and 2) and 14-O-a-and 14-O-b-L-arabinofuranosides(3 and 4), by spectroscopic and chemical methods including 2D NMR experiments and acid hydrolysis. Compounds 1–4 represent the first examples of glycosidic diterpenoid alkaloids.     

Synthetic study of biphenylquinolizidine alkaloids I. Asymmetric total synthesis of lasubine I featuring organocatalyzed asymmetric intramolecular aza-Michael addition

A new procedure for the asymmetric total synthesis of lythraceous alkaloids with a 4-arylquinolizidine skeleton was developed, which involved an organocatalyzed asymmetric intramolecular aza-Michael addition.     

Anti-inflammatory chromone alkaloids and glycoside from Dysoxylum binectariferum

Herein we report isolation of a new chromone alkaloid chrotacumine K (12) from fruits and a chromone glycoside schumaniofioside A (13) from leaves of Dysoxylum binectariferum Hook f. Schumaniofioside A is reported for the first time from Meliaceae family. Other known alkaloids isolated include rohitukine (1) and chrotacumine E (6). The structure of new alkaloid 12 was elucidated on the basis of extensive 1D and 2D NMR analysis, synthesis and chemical hydrolysis. Chemically, chrotacumine K (12) is a 3′-O-acetyl rohitukine which on chemical or enzymatic hydrolysis produces rohitukine. The new alkaloid 12 is also present in seeds and stem-barks of this plant. The glycoside schumaniofioside A (13) is present only in leaves, and in abundance (～1% w/w of dried leaves). The isolated compounds and extracts were evaluated for in vitro effect on the proinflammatory cytokines (TNF-α and IL-6) in human monocytic THP-1 cells. The alkaloid 12 displayed potent inhibition (57%) of TNF-α at 0.3 µM, and was non-toxic to THP-1 cells up to 40 µM, indicating its excellent therapeutic window. Furthermore, a nitrobenzoyl ester analog 15e showed better inhibition of IL-6 than parent natural product chrotacumine K.     

有机催化吲哚碳环上的不对称Friedel⁃Crafts烷基化反应

将金鸡纳碱衍生物双功能催化剂用于有机催化羟基吲哚与靛红的不对称Friedel-Crafts反应, 筛选出最佳反应条件: 催化剂为5%(摩尔分数)6′-脱甲基奎尼丁(1b), 溶剂为四氢呋喃, 反应温度 0 ℃. 以67%~91%的产率和最高达97%的对映选择性获得了苯环上取代的羟基烷基化产品. 拓宽了该反应的催化剂类型和底物范围.     

First total synthesis of isoquinolinone alkaloid marinamide and its methyl ester

The first total synthesis of isoquinolinone alkaloid marinamide 1 and its methyl ester 2 was described. The key steps involved a regioselective Frieclel-Crafts reaction of 1-benzyl-1H-pyrrole to form the intermediate 8.     

New reaction of formation of the fused tricyclic bispyrroloquinone ring system

A one-pot procedure to difunctionalized fused tricyclic bispyrroloquinone derivatives involving the condensation of N-tosylindoledione and α-ketoamines is described.     

Investigation of Functionalized α‐Chloroalkyllithiums for a Stereospecific Reagent‐Controlled Homologation Approach to the Analgesic Alkaloid (−)‐Epibatidine

Four putative functionalized α‐chloroakyllithiums RCH₂CHLiCl, where R=CHCH₂ ( 18 a ), CCH ( 18 b ), CH₂OBn ( 18 c ), and CH[O(CH₂)₂O] ( 18 d ), were generated in situ by sulfoxide–lithium exchange from α‐chlorosulfoxides, and investigated for the stereospecific reagent‐controlled homologation (StReCH) of phenethyl and 2‐chloropyrid‐5‐yl ( 17 ) pinacol boronic esters. Deuterium labeling experiments revealed that α‐chloroalkyllithiums are quenched by proton transfer from their α‐chlorosulfoxide precursors and it was established that this effect compromises the yield of StReCH reactions. Use of α‐deuterated α‐chlorosulfoxides was discovered to ameliorate the problem by retarding the rate of acid‐base chemistry between the carbenoid and its precursor. Carbenoids 18 a and 18 b showed poor StReCH efficacy, particularly the propargyl group bearing carbenoid 18 b , the instability of which was attributed to a facile 1,2‐hydride shift. By contrast, 18 d , a carbenoid that benefits from a stabilizing interaction between O and Li atoms gave good StReCH yields. Boronate 17 was chain extended by carbenoids 18 a , 18 b , and 18 d in 16, 0, and 68 % yield, respectively; α‐deuterated isotopomers D ‐ 18 a and D ‐ 18 d gave yields of 33 and 79 % for the same reaction. Double StReCH of 17 was pursued to target contiguous stereodiads appropriate for the total synthesis of (?)‐epibatidine ( 15 ). One‐pot double StReCH of boronate 17 by two exposures to (S)‐D ‐ 18 a (≤66 % ee), followed by work‐up with KOOH, gave the expected stereodiad product in 16 % yield (d.r.～67:33). The comparable reaction using two exposures to (S)‐D ‐ 18 d (≤90 % ee) delivered the expected bisacetal containing stereodiad (R,R)‐DD ‐ 48 in 40 % yield (≥98 % ee, d.r.=85:15). Double StReCH of 17 using (S)‐D ‐ 18 d (≤90 % ee) followed by (R)‐D ‐ 18 d (≤90 % ee) likewise gave (R,S)‐DD ‐ 48 in 49 % yield (≥97 % ee, d.r.=79:21). (R,S)‐DD ‐ 48 was converted to a dideuterated isotopomer of a synthetic intermediate in Corey’s synthesis of 15 .     

金鸡纳碱衍生物修饰的负载铱催化剂催化芳香酮不对称加氢

以金鸡纳碱衍生物作为手性修饰剂, 研究了三苯基膦稳定的Ir/SiO₂催化剂催化芳香酮多相不对称加氢. 通过电感耦合等离子体原子发射发谱(ICP-AES)、高分辨透射电镜(HRTEM)、X 射线光电子能谱(XPS)、Brunauer-Emmett-Teller (BET)比表面积测试等固体表面分析手段对负载铱催化体系进行了表征; 利用红外(IR)光谱、固体核磁共振(NMR)等分析手段初步表征了负载铱多相催化体系中手性修饰剂-金属-稳定剂在载体上的相互作用; 利用“均相与多相催化体系的对比”、“催化剂稳定性实验”、“汞中毒实验”等方法阐明了手性修饰的负载铱催化体系是多相催化体系. 还考察了稳定剂种类、修饰剂种类、金属负载量、溶剂、碱添加剂种类等因素对不对称加氢反应的影响. 结果表明, 金鸡纳碱衍生物对Ir/SiO₂催化剂具有较好的修饰作用, 在优化反应条件下苯乙酮及其衍生物加氢反应的对映选择性为52%-96%, 4-乙酰基吡啶、2-乙酰基噻吩及2-乙酰基呋喃加氢反应的对映选择性可分别达到74%、75%及63%.     

Four new compounds from Neoboletus magnificus

Abstract

Four new compounds, compounds 1, 2, 4, 6, along with two known compounds 3, 5, were isolated from the methanol extract of the fruiting body of Neoboletus magnificus. The structures of compounds were elucidated by HRMS and NMR spectroscopic methods. The in vitro anti-inflammatory activity of the isolated compounds was evaluated.