Refine
Has Fulltext
- no (4)
Year of publication
- 2012 (4) (remove)
Document Type
- Article (4)
Language
- English (4)
Is part of the Bibliography
- yes (4)
Keywords
- Access control (1)
- Carboxylic -acids (1)
- Data federation (1)
- Information integration (1)
- Lactones (1)
- Macrocycles (1)
- Metathesis (1)
- Natural products (1)
- Product lifecycle management (1)
- Semantic data (1)
Institute
alpha,beta-Unsaturated d-lactones are accessible via a sequential ring-closing metathesis (RCM) double-bond migration reaction starting from butenoates of allyl alcohols. This approach proceeds efficiently with lower catalyst loadings and higher initial substrate concentrations compared to the alternative RCM of acrylates derived from homoallylic alcohols.
Information integration across company borders becomes increasingly important for the success of product lifecycle management in industry and complex supply chains. Semantic technologies are about to play a crucial role in this integrative process. However, cross-company data exchange requires mechanisms to enable fine-grained access control definition and enforcement, preventing unauthorized leakage of confidential data across company borders. Currently available semantic repositories are not sufficiently equipped to satisfy this important requirement. This paper presents an infrastructure for controlled sharing of semantic data between cooperating business partners. First, we motivate the need for access control in semantic data federations by a case study in the industrial service sector. Furthermore, we present an architecture for controlling access to semantic repositories that is based on our newly developed SemForce security service. Finally, we show the practical feasibility of this architecture by an implementation and several performance experiments.
Enantioselective total syntheses of both enantiomers of the recently isolated decanolide natural product seimatopolide A are described. The C-2-symmetric building blocks (R,R)-hexa-1,5-diene-3,4-diol (derived from D-mannitol) and its enantiomer (derived from L-(+)-tartrate) serve as key starting materials, which are elaborated in a bidirectional way using a selective mono-cross-metathesis, regio- and stereoselective epoxidation, and regioselective reductive epoxide opening to furnish the first fragment. Both enantiomers of the second fragment, 3-hydroxypent-4-enoic acid, were conveniently obtained through a lipase-catalyzed kinetic resolution and merged with the first fragment via Shiina esterification. An E-selective ring-closing metathesis was used to access the 10-membered lactone. A comparison of the specific optical rotations of synthetic seimatopolides with those reported for the natural product suggests that the originally assigned (3R,6R,7R,9S)-configuration should be corrected to (3S,6S,7S,9R).
A one-flask reaction sequence comprising ring closing metathesis (RCM) of butenoates derived from allylic alcohols and a base-mediated ring opening gives 2Z,4E-configured dienoic acids in high yields and stereoselectivities. Application of the method to the synthesis of the natural product fusanolide A suggests that the originally published structure was erroneously assigned and should be revised.