天然产物Kinsenoside的全合成研究

以5-(R)-[(1R，2S，5R)-孟氧基]-2(5H)-呋喃酮为关键手性合成子，完成了具有抗高血脂活性的天然产物kinsenoside的全合成研究。     

Brefeldin A全合成研究新进展

Brefeldin A(布雷菲德菌素甲)是一种天然抗生素, 最早发现于1958年, 许多种微生物中都能产生该化合物. 由于其有趣的结构和显著的抗真菌、抗病毒、抗肿瘤等生物活性, 该化合物很早就引起合成化学家们的注意. 到目前为止, 文献中有报道的全合成和表观合成已有30多种. 对近十年来的全合成及部分表观合成进行了综述, 对各路线的主要优缺点也进行了简要的分析. 一些类似物的合成也一并予以简介.     

Total Synthesis of Siomycin A: Completion of the Total Synthesis

The total synthesis of siomycin A ( 1 ), a representative compound of the thiostrepton family of peptide antibiotics, was achieved by incorporating the five synthetic segments A ( 2 ), B ( 3 ), C ( 4 ), D ( 5 ), and E ( 6 ). The dehydropiperidine segment A ( 2 ) was esterified with the dihydroquinoline segment C ( 4 ), and the subsequent coupling with the β‐phenylselenoalanine dipeptide segment D ( 5 ) at the segment C portion followed by lactamization between the segments A and D gave segment A‐C‐D ( 27 ). This was amidated with the pentapeptide segment B ( 3 ) at the segment A portion followed by one‐pot cyclization (between segments A and B) and elongation (with the β‐phenylselenoalanine dipeptide segment E ( 6 ) at the segment A portion), thus furnishing siomycin A ( 1 ).     

天然产物goodyeroside A的全合成研究

以5-(S)-(d-盖氧基)-2(5H)-呋喃酮为起始原料．对具有肝保护活性的天然产物goodyeroside A进行了全合成研究。将合成所得目标产物的比旋光值及光谱数据与天然产物的数值相比较，两者一致，证明两者的结构与构型相同。     

平板霉素的全合成研究综述

平板霉素由于其强有力的抗菌能力、全新的作用机理和新颖的分子结构, 自2006年被发现起就引起了合成化学家们的广泛关注. 对平板霉素的全合成及其结构类似物的合成进行了综述和介绍.     

Synthetic Studies of the Zoanthamine Alkaloids: Total Synthesis of Zoanthenol Based on an Isoaromatization Strategy

The total synthesis of zoanthenol, a unique aromatic member of the zoanthamine alkaloids, which has exhibited potent anti‐platelet activities on human platelet aggregation, is described in full detail. The key step involves a Brønsted acid‐promoted isoaromatization in the AB ring system to install the crucial aromatic ring. We have not only succeeded in the first total synthesis of zoanthenol, but also established an alternative efficient synthetic route from the commercially available norzoanthamine hydrochloride to zoanthenol.     

Evolution of a Synthetic Strategy for Garsubellin A

Garsubellin A is a thirty-carbon meroterpenoid capable of enhancing the enzyme choline acetyltransferase whose decreased level is associated with the symptoms of Alzheimer's disease. Due to the potentially useful biological activity along with the novel molecular architecture, this plant metabolite has remained a popular synthetic target. Herein we report a full account of our synthetic investigations that have led to the enantioselective total synthesis of garsubellin A, establishing its absolute stereostructure. The protecting group-free, twelve-step synthetic route has enabled the syntheses of the natural (−)-garsubellin A and its unnatural (+)-antipode.     

Tackling the Challenges in the Total Synthesis of Landomycin A

The twists and turns toward the total synthesis of landomycin A, a prominent angucycline hexasaccharide antibiotic, in particular those toward the stereoselective construction of the di‐ and trideoxyglycosidic linkages, are described.     

Design of a Functional Chromene-Type Kobayashi Precursor: Gram-Scale Total Synthesis of Natural Xanthones by Highly Regioselective Aryne Annulation

The 2,2-dimethyl-2H-chromene motif is widely found in many bioactive molecules, and is a privileged structure in the pharmaceutical arena. We have developed a concise and regioselective approach to chromenes and chromanes through an aryne-based synthetic strategy. A practical, gram-scale synthetic route to a chromene-type aryne precursor was explored. Subsequently, cyclization under mild conditions afforded tetracyclic xanthone skeletons with excellent regioselectivity. Our approach provides a concise strategy for the gram-scale synthesis of chromene-type xanthones such as 6-deoxyisojacareubin, cylindroxanthone D, staudtiixanthone D, brasilixanthone A and cudracuspixanthone O.     

Evolution of a Strategy for the Total Synthesis of (+)-Cornexistin

Herein is given a full account of the evolution of the first total synthesis of (+)-cornexistin. Initial efforts were based on masking the reactive maleic anhydride moiety as a 3,4-substituted furan and on forming the nine-membered carbocycle in an intramolecular Conia-ene or Nozaki–Hiyama–Kishi (NHK) reaction. Those strategies suffered from low yields and were jeopardized by a late-stage installation of the Z-alkene, as well as the stereocenters along the eastern periphery. These issues were addressed by employing a chiral-pool strategy that involved construction of the crucial stereocenters at C2, C3 and C8 at an early stage with installation of the maleic anhydride as late as possible. The successful approach featured an intermolecular NHK coupling to install the Z-alkene, a syn-Evans-aldol reaction to forge the stereocenters along the eastern periphery, an intramolecular allylic alkylation to close the nine-membered carbocycle, and a challenging stepwise hydrolysis of a β-keto nitrile to furnish the maleic anhydride.     

苯乙烯内酯类天然产物的全合成进展

结合本研究小组的相关课题工作，综述了苯乙烯内酯类天然产物全合成方法的 研究进展。主要包括以呋喃甲醇类化合物的氧化重排反应、烯烃复分解环化反应（ RCM）和酸催化的酯化关环等作为关键反应的方法。     

An Expeditious Route for the Total Synthesis of Pondaplin Isolated from Annona glabra

A novel cyclic prenylated phenylpropanoid, pondaplin 1, was first synthesized in 26% overall yields through an expeditious route (7 steps) that employed highly regio- and stereoselective phenyltellurenylation to arylacetylene and palladium (Ⅱ) chloride-catalyzed carbonylation of hydroxy styryl phenyl telluride as key steps.     

Total Synthesis of Marinomycin A Based on a Direct Dimerization Strategy

The asymmetric total synthesis of (+)‐marinomycin A, a 44‐membered macrodiolide antitumor agent and antibiotic isolated from a marine actinomycete, Marinispora strain CNQ‐140, is reported. The key features of the synthesis include the highly convergent stereocontrolled construction of the monomeric hydroxy salicylate starting from asymmetric epoxidation of the σ‐symmetrical dialkenyl carbinol, and an unprecedented direct dimerization through NaHMDS‐promoted double transesterification.     

Total Synthesis of Aspidosperma and Strychnos Alkaloids through Indole Dearomatization

Monoterpenoid indole alkaloids are the major class of tryptamine-derived alkaloids found in nature. Together with their structural complexity, this has attracted great interest from synthetic organic chemists. In this Review, the syntheses of Aspidosperma and Strychnos alkaloids through dearomatization of indoles are discussed.     

百部生物碱的全合成

百部生物碱是从直立百部(Stemona sessilifolia)和其近缘植物的根部分离得到一类生物碱。在分子结构上,这类生物碱通常具有[1, 2-b]吡咯并[1, 2-a]氮杂卓的母核结构,并且由于在母核的多个位置有不同的取代基,从而表现出结构及生物活性的多样性,因而百部生物碱的全合成研究引起国内外化学家的关注。但是由于百部生物碱结构中具有复杂的多环结构及多个手性中心,此类天然产物的全合成研究具有较大的挑战。近年来,化学家们相继开发并应用高对映选择性的反应及串联反应等高效的策略,完成了多个百部生物碱的全合成研究,为百部生物碱进行深入生物活性研究及开发利用奠定了坚实的基础。本文基于本课题组的相关研究内容,综述了各种类型百部生物碱近年来的全合成研究进展。     

Solid‐Phase Total Synthesis of Yaku'amide B Enabled by Traceless Staudinger Ligation

We report a solid‐phase strategy for total synthesis of the peptidic natural product yaku'amide B ( 1 ), which exhibits antiproliferative activity against various cancer cells. Its linear tridecapeptide sequence bears four β,β‐dialkylated α,β‐dehydroamino acid residues and is capped with an N‐terminal acyl group (NTA) and a C‐terminal amine (CTA). To realize the Fmoc‐based solid‐phase synthesis of this complex structure, we developed new methods for enamide formation, enamide deprotection, and C‐terminal modification. First, traceless Staudinger ligation enabled enamide formation between sterically encumbered alkenyl azides and newly designed phosphinophenol esters. Second, application of Eu(OTf)₃ led to chemoselective removal of the enamide Boc groups without detaching the resin linker. Finally, resin‐cleavage and C‐terminus modification were simultaneously achieved with an ester–amide exchange reaction using CTA and AlMe₃ to deliver 1 in 9.1 % overall yield (24 steps from the resin).