Facile Syntheses of (±)-Curcuphenol, (±)-Curcudiol, (±)-Curcuhydroquinone,and (±)-Curcuquinone

The syntheses of (±)-curcuphenol 1, (±)-curcudiol 2, (±)-curcuhydroquinone 3, and (±)-curcuquinone 4 have been achieved. The key steps involved in the syntheses were the Reformatsky reaction and hydrogenation reaction.     

Photochemical Symthesisof Aporphines: (±)-Thaliporphime. (±)-N-Nethyllaurotetanineand(±)-Isoboldime

Aporphines, (±)-thaliporphine (1). (±)-N-methyllaurotetatine (2), and (±)-isoboldine (3) were synthesised using photochemical cyclization as the key step.     

Total synthesis of (±)-maistemonine, (±)-stemonamide, and (±)-isomaistemonine

A full account of the total synthesis of (±)-maistemonine, (±)-stemonamide, and (±)-isomaistemonine is presented. Two approaches have been developed to construct the basic pyrrolo[1,2-a]azepine core of the Stemona alkaloids, featuring a tandem semipinacol/Schmidt rearrangement of a secondary azide and a highly stereoselectively desymmetrizing intramolecular Schmidt reaction, respectively. To build the common spiro-γ-butyrolactone, a new protocol was carried out by utilizing an intramolecular ketone-ester condensation as the key transformation. The vicinal butyrolactone moiety of (±)-maistemonine was stereoselectively introduced via a one-pot procedure involving the epimerization at C-3 and carbonyl allylation/lactonization. Moreover, (±)-stemonamide was divergently synthesized from a common intermediate, and (±)-isomaistemonine was obtained via the epimerization of (±)-maistemonine at C-12.     

Photochemical Synthesis of Aporphines: (±)-Glaucine, (±)-Norglaucine and (±)-Dehydronorglaucine

Photochemical cyclization of 3 afforded 5, 4 and 8.5 on LAH reduction furnished (±)-glaucine (6) and on treatment with ethanolic HCl afforded (±)-norglaucine (7). 10 obtained by the photocyclization of 9 was converted into 7 and 11 via 12.     

Total Synthesis of (±)-Boschnialactone and (±)-Tetrahydroanhydrodesoxyaucubigenin

A total synthesis of (±)-boschnialactone ( 1 ) and (±)-tertahydroanhydrodesoxyaucubigenin ( 2 ) is described and trisubstitued cyclopentenoid 3 is a key intermediate.     

(±)-Seudenol和(±)-Frontalin的简便合成

从易得的油酸出发 ,经关键中间体 2 ,6 庚二酮合成了云杉红翅小蠹集合信息素 (± ) Seudenol (3 甲基 2 环己烯 1 醇 )和南部松小蠹集合信息素 (± ) Frontalin (1 ,5 二甲基 6,8 二氧双环 [3 .2 .1 ]辛烷 )。所合成化合物的结构经IR、MS、1HNMR和13CNMR证实。     

Total synthesis of (±)-maistemonine and (±)-stemonamide

The first total synthesis of polycyclic Stemona alkaloid maistemonine has been achieved. The efficient approach features a stereoselective intramolecular Schmidt reaction, a ketone-ester condensation, and a Reformatsky reaction. Additionally, another Stemona alkaloid stemonamide was divergently synthesized from a common intermediate.     

Total syntheses of (±)-securinine and (±)- allosecurinine

Total syntheses of (±)-securinine and (±)-allosecurinine that employ a tandem rhodium carbenoid-initiated Claisen/α-ketol rearrangement sequence as a key step are described.     

(±)-Diplacone与(±)-3'-O-methyldiplacone的全合成

以廉价的香草醛,3,4-二羟基苯甲醛和2,4,6-三羟基苯乙酮为初始原料,经过C-香叶基化、羟基保护、羟醛缩合、脱去保护基以及催化环化等步骤,以11%和20%的总收率实现了两个天然香叶基黄烷酮(±)-diplacone与(±)-3′-O-methyldiplaone的首次全合成,其结构经¹H NMR, IR和MS表征。     

(±)-Malaysianone A和(±)-Tanariflavanones B的全合成

以取代苯乙酮和5-醛基-8-甲氧甲氧基-2-甲基-2-(4'-甲基-3'-戊烯基)-二氢-1-苯并吡喃为原料,经羟醛缩合反应制得两个中间体——7,2',4'-三甲氧甲氧基-6'-羟基-2-甲基-2-(4'-甲基-3'-戊烯基)-二氢-1-苯并吡喃查尔酮(3a)和7,2',4'-三甲氧甲氧基-5'-异戊烯基-6'-羟基-2-甲基-2-(4'-甲基-3'-戊烯基)-二氢-1-苯并吡喃查尔酮(3b);3a经环合和脱保护基反应合成了(±)-Malaysianone A(4a),产率12.9%;3b经脱保护基和环合反应合成了(±)-Tanariflavanones B(4b),产率5.2%。4a和4b的结构经1H NMR,13C NMR和HR-ESI-MS确证。     

The Total Synthesis of (±)-Hinesol and (±)-Agarospirol

Eversinceβ-vetivoneanditscongenerswererecognizedtohavespiro[4,5]decaneratherthanthehydroazuleneskeleton,[1]themembersofthisclasshavebecomeafavoritetargetforsynthesis.Herein.weshowafacileconversionofthemajorphotoproductformedinthereactionofmethyl2,4-dioxopentancate(1)with1,5-dimethyl-6-methylenecyclochexene(2)[2]intovetispiranederivatives,hinesol(3),ametaboliteofAtractylodeslancea[3,4],andagarospirol(4)foundinAquilariaagollocha,[5]inracemicforms,respectively.WhenanEtoAsolutionof1and2wasintema…     

Enzymatic resolution of (±)-cis- and (±)-trans-1-aminoindan-2-ol and (±)-cis- and (±)-trans-2-aminoindan-1-ol

Pseudomonas cepacia lipase (PSL) efficiently catalyses the kinetic resolution of (±)-cis- and (±)-trans-1-aminoindan-2-ol through the O-acylation reaction of the corresponding N-benzyloxycarbonyl derivative using vinyl acetate as the acyl donor. In a similar way, cis-N-Cbz-2-aminoindan-1-ol is resolved when isopropenyl acetate is used as the acylating agent. The enantioselectivity of the reaction was lower for (±)-trans-N-Cbz-2-aminoindan-1-ol due to the different steric requirements for the two conformers of this substrate.     

(±)-Shegansu B,Gnetuhainin F, (±)-Maackin A与(±)-Cassigarol E的全合成

对四种天然二聚二苯乙烯类化合物Shegansu B (1), Gnetuhainin F (1a), Maackin A (2)以及Cassigarol E (3)的全合成进行了研究. 以3,5-二羟基苯甲酸(4)为起始原料, 经六步反应制得异丹叶大黄素(13)和白皮杉醇(14), 在HRP/H₂O₂酶催化氧化体系中, 13和14分别进行自身的氧化偶联得到各自的二聚产物. 首次完成了1a, (±)-2和(±)-3的全合成, 并以较文献报道为高的氧化偶联产率合成了(±)-1.     

Total synthesis of (±)-cycloclavine and (±)-5-epi-cycloclavine

Novel routes to the naturally occurring indole alkaloid cycloclavine and its unnatural C(5)-epimer are described. Key features include the rapid construction of the heterocyclic core segments by two Diels-Alder reactions. An indole annulation was accomplished by a late-stage intramolecular Diels-Alder furan cycloaddition, and a methylenecyclopropane dienophile was used for a stereoselective intramolecular [4 + 2] cycloaddition to give the cyclopropa[c]indoline building block present in cycloclavine.     

(±)-Cycloaltilisin 7和(±)-Poinsettifolin B的首次全合成

Cycloaltilisin 7是从桑科植物面包树(Artocarpus altilis)的芽中分离出的一种新异戊烯基黄烷酮,具有组织蛋白酶K抑制活性;Poinsettifolin B也是从桑科琉桑属植物Dorstenia poinsettifolia中分离出的一种新的香叶基查尔酮,Dorstenia poinsettifolia是原产于喀麦隆潮湿森林的草本植物,用于民间雅司病和伤口感染的治疗,对治疗皮肤病也有潜在功效.以廉价的羟苯乙酮和羟苯甲醛为原料,用简单温和的方法完成了这两种天然产物的首次全合成.所有新化合物的结构都经过HRMS,1H NMR和13C NMR的确认.     

(±)-Galbulin和(±)-8,8′-epi-aristoligone的全合成

(±)-galbulin和(±)-8,8′-epi-aristoligone属于苯代四氢萘型木脂素类化合物,具有广泛的生物活性.以3,4-二甲氧基苯乙酸为起始原料,采用Horner-Wadsworth-Emmons反应和Friedel-Crafts反应为关键步骤,经8步得到了(±)-galbulin,并通过将(±)-galbulin苄位氧化得到(±)-8,8′-epi-aristoligone.该法操作简单,路线较短,为苯代四氢萘型木脂素化合物的合成提供了参考.     

First total synthesis of (±)-puyanin and (±)-4'-O-methylbonannione

<正>A facile approach for the first total synthesis of two naturally occurring geranylated flavonoids,(±)-puyanin 1 and(±)-4'-O- methylbonannione 2 has been obtained with total yield 27%and 21%,respectively.The key steps were regioselective cyclization of geranylated trihydroxychalcone and regioselective geranylation of 2,4,6-trihydroxyacetophenone.     

Synthesis of (±)-Bimatoprost

A general synthetic approach has been developed for the synthesis of a key intermediate (6) that can be elaborated into several ophthalmic prostaglandins and their derivatives. Using these strategy, we have obtained (±)-bimatoprost (1) and its analog, (±)-homobimatoprost (5).     

(±)-Mesembrine的全合成

以3-乙氧基-2-环己烯酮羰基邻位芳基化反应与Tsuji-Trost反应的串联反应作为关键步骤来构筑季碳中心,完成了番杏科生物碱Mesembrine的全合成.从商品化原料出发经6步反应以17.8%的总收率合成得到(±)-Mesembrine.