A radical cyclisation based strategy to cuparenoids; synthesis of (±)-α-cuparenone, (±)-epilaurene and laurenes

Mercuric acetate catalysed one pot Claisen rearrangement of the cinnamyl alcohol Image , generated the pent-4-enal Image , which on homologation resulted the hex-5-enal Image . Radical cyclisation of the radical anion derived from Image , followed by oxidation provided the ketone mixture Image , a known precursor to the sesquiterpenes (Image )-α-cuparenone (Image ), (Image )-epilaurene (Image ) and laurene (Image )

A Strategy for Conserving the Biodiversity of the Uttara Kannada District in South India

Taking the various values ascribed to biodiversity as its point of departure rather many years ago, the present study aims at deriving a conservation strategy for Uttara Kannada. This hilly district, with the highest proportion of its area under forests in South India, is divided into five ecological zones: coastal, northern evergreen, southern evergreen, moist deciduous, and dry deciduous. The heavily-populated coastal zone includes mangrove forests and estuarine wetlands. The evergreen forests are particularly rich in the diversity of plant species which they support - including wild relatives of a number of cultivated plants. They also serve a vital function in watershed conservation. The moist deciduous forests are rich in bird species; both moist and dry deciduous forests include a number of freshwater ponds and lakes that support a high diversity of aquatic birds.Reviewing the overall distribution of biodiversity, we identify specific localities - including estuaries, evergreen forests, and moist deciduous forests - which should be set aside as Nature reserves. These larger reserves must be complemented by a network of traditionally-protected sacred groves and sacred trees that are distributed throughout the district and that protect today, for instance, the finest surviving stand of dipterocarp trees.We also spell out the necessary policy-changes in overall development strategy that should stem the ongoing decimation of biodiversity. These include (1) revitalizing community-based systems of sustainable management of village forests and protection of sacred groves and trees; (2) reorienting the usage-pattern of reserve forests from production of a limited variety of timber and softwood species for industrial consumers, to production of a larger diversity of non-wood forest produce of commercial value to support the rural economy; (3) utilizing marginal lands under private ownership for generating industrial wood supplies; and (4) provision of incentives for in situ maintenance of land-races of cultivated plants - especially evergreen, fruit-yielding trees - by the local people.It is proposed that this broad framework be now taken to the local communities, and that an action-plan be developed on the basis of inputs provided - and initiatives taken - by them.

A monolithic strategy for fluid-structure interaction problems

In this work, we present a new monolithic strategy for solving fluid-structure interaction problems involving incompressible fluids, within the context of the finite element method. This strategy, similar to the continuum dynamics, conserves certain properties, and thus provides a rational basis for the design of the time-stepping strategy; detailed proofs of the conservation of these properties are provided. The proposed algorithm works with displacement and velocity variables for the structure and fluid, respectively, and introduces no new variables to enforce velocity or traction continuity. Any existing structural dynamics algorithm can be used without change in the proposed method. Use of the exact tangent stiffness matrix ensures that the algorithm converges quadratically within each time step. An analytical solution is presented for one of the benchmark problems used in the literature, namely, the piston problem. A number of benchmark problems including problems involving free surfaces such as sloshing and the breaking dam problem are used to demonstrate the good performance of the proposed method. Copyright (C) 2010 John Wiley & Sons, Ltd.

Radical Annulation Strategy to Chiral Pupukeanones: Total Synthesis of (+)-10-ex&l(- Naphthyl)pupukean-9-onea nd (+)-lO-exo-l(- Naphthyl)-5-epipupukean-9-ones1

Intramolecular alkylation reaction of the bromoenone 12, obtained from S-carvone in three steps, furnished the bicyclo[2.2.2]octenone 13. Contrary to the anticipated radical annulation reaction, the bicyclic bromides 14 and 15, obtained from the enone 13, generated exclusively the cyclopropane product 18 via a 3-exo-trig radical cyclization on reaction with nBu3SnH and AIBN, even in the presence of a large excess of a radicophile. On the other hand, bromoenone 24, synthesized from R-carvone via S-naphthylcarvone 21, underwent radical annulation reaction in the presence of radicophiles to furnish the isotwistanes 25-28 in a regio- and stereospecific manner. Hydrogenation of the olefin 34, obtained from the diketone 27 via a regiospecific Wittig reaction, furnished the naphthyl-5-epipupukean-9-one 33, whereas stereoselective hydrogenation of the enone 36, prepared from the keto ester 25 via a Grignard reaction and dehydration sequence, generated the naphthylpupukeanone 32.

A regiospecific radical annulation strategy to functionalised chiral bicyclo[3.3.l]nonanes

A radical annulation, i.e. an intermolecular radical Michael addition followed by an intramolecular Michael addition of the resultant radical (radical cyclisation) has been employed for the construction of chiral functionalised bicyclo[3.3,1]-nonanes. Thus reaction of carvone hydrohalides 7 with (n)Bu(3)SnH and AIBN in the presence of excess of radicophiles 4 furnished, regiospecifically bicyclo[3.3.1]nonanes 8-14, introducing three new chiral centres in a stereoselective manner. Analogously the bromide 18 generated the bridgehead substituted bicyclo[3.3.1]-nonanes 19-21.

An Efficient Random Walk Strategy for Sampling Based Robot Motion Planners

Sampling based planners have been successful in path planning of robots with many degrees of freedom, but still remains ineffective when the configuration space has a narrow passage. We present a new technique based on a random walk strategy to generate samples in narrow regions quickly, thus improving efficiency of Probabilistic Roadmap Planners. The algorithm substantially reduces instances of collision checking and thereby decreases computational time. The method is powerful even for cases where the structure of the narrow passage is not known, thus giving significant improvement over other known methods.

A simple strategy for spirocyclopentannullation of cyclic ketones. Formal total synthesis of (+/-)-acorone

A general and simple methodology for spirocyclopentannulation of cyclic ketones (or 4,4-disubstituted cyclopentenones from acyclic ketones) and its application in the synthesis of the spirodienone 7 via a prochiral precursor constituting a formal total synthesis of (+/-)-acorone (6), are described.

Towards the total synthesis of tashironin related allo-cedrane natural products: further exploitation of the oxidative dearomatization-IMDA-RCM triad based strategy

Synthetic studies directed towards allo-cedrane based, tashironin sibling natural products, involving some deft functional group manipulations on a preformed tetracyclic scaffold, are delineated. (C) 2011 Elsevier Ltd. All rights reserved.

A new strategy for the alpha-vinylation of ketones: Application to an enantioselective synthesis of sesquiterpene (+)-alpha-elemene

A new, simple and preparatively useful protocol for the construction of a-vinyl ketones, particularly those bearing a quaternary carbon centre, from the corresponding alkenes has been devised. Our four-step strategy consists of dichloroketene addition, base catalysed ring contraction to 'push-pull' cyclopropane esters, reduction and eliminative cyclopropane fragmentation to unravel the a-vinyl ketone moiety. The generality of this approach has been demonstrated with a few representative olefins and good regio- and stereocontrol has been observed. As an application of this methodology, an enantioselective synthesis of sesquiterpene hydrocarbon (+)-alpha-elemene (42) from R-(+)-limonene (43) has been accomplished.

Shape and size mimicry in the design of ternary molecular solids: towards a robust strategy for crystal engineering

2- and 5-methylresorcinol form co-crystals with 4,4'-bipyridine in which some of the bipyridine molecules are loosely bound. These molecules can be replaced with other molecules of a similar shape and size to give a general method for the engineering of a ternary co-crystal.

Nanostructuration via solid state transformation as a strategy for improving the thermoelectric efficiency of PbTe alloys

The approach taken in this paper in order to modify the scattering features of electrons and phonons and improve the figure of merit (ZT) of thermoelectric PbTe is to alter the microstructure at constant chemistry. A lamellar pattern of PbTe/GeTe at the nano- and microscale was produced in Pb(0.36)Ge(0.64)Te alloy by the diffusional decomposition of a supersaturated solid solution. The mechanism of nanostructuration is most likely a discontinuous spinodal decomposition. A simple model relating the interface velocity to the observed lamellar spacing is proposed. The effects of nanostructuration in Pb(0.36)Ge(0.64)Te alloy on the electrical and thermal conductivity, thermopower and ZT were investigated. It was shown that nanostructuration through the formation of a lamellar pattern of PbTe/GeTe is unlikely to provide a significant improvement due to the occurrence of discontinuous coarsening. However, the present study allows an analysis of possible strategies to improve thermoelectric materials via optimal design of the microstructure and optimized heat treatment. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Modern energy access to all in rural India: An integrated implementation strategy

Expanding energy access to the rural population of India presents a critical challenge for its government. The presence of 364 million people without access to electricity and 726 million who rely on biomass for cooking indicate both the failure of past policies and programs, and the need for a radical redesign of the current system. We propose an integrated implementation framework with recommendations for adopting business principles with innovative institutional, regulatory, financing and delivery mechanisms. The framework entails establishment of rural energy access authorities and energy access funds, both at the national and regional levels, to be empowered with enabling regulatory policies, capital resources and the support of multi-stakeholder partnership. These institutions are expected to design, lead, manage and monitor the rural energy interventions. At the other end, trained entrepreneurs would be expected to establish bioenergy-based micro-enterprises that will produce and distribute energy carriers to rural households at an affordable cost. The ESCOs will function as intermediaries between these enterprises and the international carbon market both in aggregating carbon credits and in trading them under CDM. If implemented, such a program could address the challenges of rural energy empowerment by creating access to modern energy carriers and climate change mitigation. (C) 2011 Elsevier Ltd. All rights reserved.

An embedded grid adaptation strategy for unstructured data based finite volume computations

A grid adaptation strategy for unstructured data based codes, employing a combination of hexahedral and prismatic elements, generalizable to tetrahedral and pyramidal elements has been developed.