Synthesis of Highly Substituted γ‐Butyrolactones by a Gold‐Catalyzed Cascade Reaction of Benzyl Esters

Easily accessible benzylic esters of 3‐butynoic acids in a gold‐catalyzed cyclization/rearrangement cascade reaction provided 3‐propargyl γ‐butyrolactones with the alkene and the carbonyl group not being conjugated. Crossover experiments showed that the formation of the new C?C bond is an intermolecular process. Initially propargylic–benzylic esters were used, but alkyl‐substituted benzylic esters worked equally well. In the case of the propargylic–benzylic products, a simple treatment of the products with aluminum oxide initiated a twofold tautomerization to the allenyl‐substituted γ‐butyrolactones with conjugation of the carbonyl group, the olefin, and the allene. The synthetic sequence can be conducted stepwise or as a one‐pot cascade reaction with similar yields. Even in the presence of the gold catalyst the new allene remains intact.     

Three Novel Eremophilanolides from Ligularia virgaurea spp. oligocephala

From the alcoholic extract of the whole plant of Ligularia virgaurea spp. oligocephala, three novel eremophilane sesquiterpene lactones, 6α, 10α-dihydroxy- 1-oxoeremophila-7(11), 8(9)-dien-8, 12-olide, 613, 10α-dihydroxy-1-oxoeremophila-7 (ll), 8 (9)-dien-8, 12-olide and 10α-hydroxy-1-oxoeremophila-7(l 1), 8(9)-dien-8, 12-olide were isolated. Their structures were elucidated by various spectroscopic methods including intensive 2D NMR techniques (COSY,HMQC, HMBC and ^1H-^1H NOESY) and HR-MS.     

An improved synthesis of rhinocerotinoic acid

The stereoselective synthesis of E-rhinocerotinoic acid has been achieved in five steps from (−)-sclareol in an overall yield of 32%. This constitutes a significant improvement on the previous synthesis of this anti-inflammatory compound.     

Two New Diterpene Acetylxylosides from Aster veitchianus

Two new acetylxylosides,ent-manool-13-O-β-D-2′-acetylxylopyranoside(1)and entmanool-13-O-β-D-2′,4′-diacetylxylopyranoside(2)were isolated from Aster veitchianus.Their structures were elucidated by spectroscopic methods.     

First Total Synthesis of 12-Hydroxy-13-methylpodocarpa-9, 11, 13-trien-3-one

12-Hydroxy-13-methylpodocarpa-9, 11, 13-trien-3-one 9 was isolated from the twigs ofCroton salutaris1. Many diterpenes exhibit significant bioactivities, such as antibac-terial and antitumour and 9 has a rare structure. In order to study the relationshipb…     

（±）—Salvinolone的全合成研究

以２－（３，４－环己基类二氧－５－异丙基）苯基乙醇（２）和３－异丙氧基－５，５－二甲基－１，３－环己烯酮（４）为原料，利用羰基α－位的烷基化反应和分子内的Ｆｒｉｅｄｅｌ－Ｃａｒｆｔｓ反应为关键步骤，经９步反应，合成了多氧芳香型三环二萜类天然产物Ｓａｌｖｉｎｏｌｏｎｅ。     

XY-ZH compounds as potential 1,3-dipoles. Part 63: Silver catalysed azomethine ylide cycloaddition—the synthesis of spiro homoserine lactone analogues

A range of room temperature 1,3-dipolar cycloaddition reactions of imines of 2-amino-γ-lactone and thiolactone, catalysed by a combination of AgOAc or Ag₂O with NEt₃ or DBU, are described. The spiro lactones/thiolactones are formed regio- and stereoselectively as single cycloadducts in good yield via the syn dipoles and an endo-transition states.     

Facile synthesis of C-aryl glycals from sugar-derived lactones

A general entry to C(1) aryl-substituted glycals from the corresponding sugar lactones is described. This approach features one-pot access to aryl glycals. A variety of aryllithium reagents can be used and the method is compatible with various 2-deoxysugar lactones.