The intramolecular Buchner reaction of α-diazo-β-ketonitriles : development and application to the total synthesis of (+)-Salvileucalin B

Since its discovery in 1896, the Buchner reaction has fascinated chemists for more than a century. The highly reactive nature of the carbene intermediates allows for facile dearomatization of stable aromatic rings, and provides access to a diverse array of cyclopropane and seven-membered ring architectures. The power inherent in this transformation has been exploited in the context of a natural product total synthesis and methodology studies.

The total synthesis work details efforts employed in the enantioselective total synthesis of (+)-salvileucalin B. The fully-substituted cyclopropane within the core of the molecule arises from an unprecedented intramolecular Buchner reaction involving a highly functionalized arene and an α-diazo-β-ketonitrile. An unusual retro-Claisen rearrangement of a complex late-stage intermediate was discovered on route to the natural product.

The unique reactivity of α-diazo-β-ketonitriles toward arene cyclopropanation was then investigated in a broader methodological study. This specific di-substituted diazo moiety possesses hitherto unreported selectivity in intramolecular Buchner reactions. This technology was enables the preparation of highly functionalized norcaradienes and cyclopropanes, which themselves undergo various ring opening transformations to afford complex polycyclic structures.

Finally, an enantioselective variant of the intramolecular Buchner reaction is described. Various chiral copper and dirhodium catalysts afforded moderate stereoinduction in the cyclization event.

Lessons from History for Transitions to a Low Carbon Economy

4 p.

Long Run Trends in the Price of Energy and Energy Services

4 p.

The Role of the Demand for Environmental Quality in Driving Transitions to Low-Polluting Energy Sources

4 p.

Divergences in the Long Run Trends in the Price of Energy and of Energy Services

32 p.

The Slow Search for Solutions: Lessons from Historical Energy Transitions by Sector and Service

28 p.

The Sustainability of `Sustainable´ Energy Use: Historical Evidence on the Relationship between Economic Growth and Renewable Energy

20 p.

Long Run Trends in Energy-Related External Costs

30 p.

The Long Run Demand for Lighting: Elasticities and Rebound Effects in Different Phases of Economic Development

25 p.

The Demand for Environmental Quality in Driving Transitions to Low Polluting Energy Sources

38 p.

Trends in Income and Price Elasticities of Transport Demand (1850-2010)

40 p.

Economics of Energy and Climate Change: Origins, Developments and Growth

27 p.

Long Run Demand for Energy Services: the Role of Economic and Technological Development

36 p.

Pathways for the uptake of dissolved organic matter (DOM) by aquatic animals

In this article, pathways from freshwater and marine environments are described. DOM is defined operationally as all the organic compounds which pass through a filter of pore size 0.45 microm., those retained on the surface of the filter being particulate organic matter (POM). DOM can be taken up directly by animals by transfer across the body wall, but more commonly DOM is obtained from ingested food. Once ingested POM from food particles are broken down in the gut, small molecules of DOM are released for transfer across the gut wall. Some ingested particles are attacked by micro-organisms living in the gut, thereby making the DOM available to the host animal. The importance of the microbial loop is discussed, as well as aggregation processes between the fractions of DOM which are more obviously particulate in nature. (DBO)

A review of current biological and recent environmental research on Lake Baikal from a British perspective

In 1990, "BICER" or the Baikal International Centre for Ecological Research was created to foster collaborative research on Lake Baikal. The British effort in BICER was initiated and is administered by the Royal Society, London. Much of the on-going research effort is now focussed on environmental change, as there is increasing concern about recent changes in the lake's unique ecosystem that could be linked with the effects of water pollution from catchment effluents. Monitoring studies of the phytoplankton in Lake Baikal's southern basin indicate that several species have increased in abundance since the mid-70's. Diatoms in Lake Baikal sediments are also being studied.