Total synthesis of (+)-cassaine via transannular Diels-Alder reaction

A full account of the total synthesis of (+)-cassaine ( 1) using the transannular Diels-Alder (TADA) reaction as the pivotal construction is described. The strategy began from Evans' oxazolidine 8, the only chiral source used for the total stereochemical outcome of the target molecule. The key intermediate 3 was obtained from 8 in 10 steps in 40% overall yield. Following extensive optimization, the coupling of 3 on both ends with another densely functional partner 2 followed by TADA reaction on macrocycle 4 cleanly furnished the tricycle 5. The stereochemical outcome in 5 was expected via a least-energetic transition state T4. A stereoselective reduction, hydroboration, and methyl cuprate 1,4-addition along with a few other functional interconversions transformed 5 into the key intermediate 37. Final tethering of dimethylaminoethyloxycarbonyl along with epimerization at C8 and alcohol deprotection at C3 yielded the natural product 1.     

Study of thermal lensing effects in a copper vapor laser

The thermal lensing effect of the Copper Vapor Laser (CVL) was studied by considering both its windows and the active medium. The equivalent combined focal length of the active medium and windows was measured to be 52 mts under operating conditions for a 35W CVL. The variation of focal length with the operating parameters was studied.     

Aircraft and crew scheduling for fractional ownership programs

Fractional aircraft ownership programs, where individuals or corporations own a fraction of an aircraft, have revolutionized the corporate aviation industry. Fractional management companies (FMC) manage all aspects of aircraft operations enabling the owners to enjoy the benefits of private aviation without the associated responsibilities. We describe here the development of a scheduling decision support tool for a leading FMC. We present mathematical models, exact and heuristic solution methods. Our computational results using real and randomly generated data indicate that these models are quite effective in finding optimal or near-optimal solutions. The first phase of the implementation of one of these models at the FMC led to a significant improvement in effective utilization of the aircraft, reduction of costs due to reduced empty moves, and hence increased profits.     

Two New Pseudoguaianolides from the Flowers of Parthenium hysterophorus

Chemical investigation on two samples of the flowers of Parthenium hysterophorus afforded two new pseudoguaianolides (one from each sample) together with several known constituents. The structures of the new compounds were established by extensive spectroscopic (1D‐ and 2D‐NMR) studies. The X‐ray crystallographic analysis of one of these compounds was also accomplished.     

Synthesis and Structural Proof of a Potent 5-Lipoxygenase Inhibitor

Abstract  

5-Lipoxygenase inhibitor 3-O-acetyl-9,11-dehydro-β-boswellic acid was detected in the extract of Boswellia serrata gum resulting from unstable 11-hydroxy precursor. It was reported more potent than other Boswellic acids in its inhibition of 5-Lipoxygenase. Here, we report the method of conversion of 3-acetoxy-β-boswellic acid to 3-O-acetyl-9,11-dehydro-β-boswellic acid, and the crystal structure of later. This compound crystallizes in orthorhombic space group P2₁2₁2₁ with cell parameters of a = 12.726(1) ?, b = 16.597(1) ?, c = 27.332(2) ?, α = β = γ = 90°, V = 5772.7(5) ?³, D _c = 1.143 Mg/m³, and Z = 8. The X-ray structure investigation indicates that the rings A, B, D and E are exhibit chair and the ring C adopts a distorted half chair conformation. The conformational difference of the two structures in the arrangement is due to crystal packing of 3-O-acetyl-9,11-dehydro-β-boswellic acid. The molecular packing is stabilized by C–H···O and O–H···O types of hydrogen bonding interactions.     

Iron(III) chloride catalysed three-component Grieco condensation: Synthesis of tetrahydropyrido[2′,3′:3,4]pyrazolo[1,5-a]pyrimidines/quinazolines

Three-component Grieco condensation reaction of 3-aminopyrazolo[3,4-b]pyridine, formaldehyde/benzaldehyde and electron rich alkenes in presence of iron(III) chloride gave tetrahydropyrido[2′,3′:3,4]pyrazolo[1,5-a]pyrimidines/quinazolines in single pot. The sequence of reactions is formation of di-azadiene in situ and the subsequent regioselective addition of alkenes in aza-Diels Alder type reaction. The structure and stereochemistry of the products were confirmed by spectral data and single crystal X-ray crystallography.     

Additive-subtractive phase-modulated speckle interferometry: Fringe visibility under partial decorrelation

Additive-subtractive phase modulated speckle interferometry (ASPMSI) is a technique that minimizes the susceptibility of speckle methods to environmental noise while providing fringes of good visibility. The method requires the acquisition of two consecutive video frames of additive-speckle images of the same two deformed states of an object at a rapid enough rate such that ambient noise is not a problem. The additive-speckle images as expected are of very poor visibility due to the presence of the self-interference term. An interframe phase-modulation is introduced and the two additive-speckle images are digitally subtracted to improve the fringe visibility by removing the self-interference term. The ASPM-SI method works with in-plane and out-of-plane deformation sensitive ESPI as well as with displacement-gradient sensitive speckle-shearing interferometry. It is shown that the ASPM-SI scheme has higher visibility than conventional additive-SI and performs consistently better than subtractive-SI schemes in the presence of partial interframe speckle decorrelating optical noise. Furthermore, it is shown that the fringe visibility of the out-of-plane displacement sensitive interferometer which uses a protected reference beam separate from the object beam can be made to be essentially unity even at complete interframe decorrelation.     

Iron-catalyzed regioselective direct oxidative aryl-aryl cross-coupling

Regioselective iron-catalyzed cross-dehydrogenative coupling (CDC) of two aromatic compounds using tert-BuOOH as oxidant under mild conditions has been reported. The direct oxidative coupling reaction is selective toward creation of a carbon-carbon bond at the position ortho to the functional groups of the substrates, completely preventing the homocoupled products. The C-C bond-forming reaction makes the method versatile, leading to functionalized 2,2' -disubstituted biaryls.     

The flow over a thin airfoil subjected to elevated levels of freestream turbulence at low Reynolds numbers

Micro Air Vehicles (MAVs) can be difficult to control in the outdoor environment as they fly at relatively low speeds and are of low mass, yet exposed to high levels of freestream turbulence present within the Atmospheric Boundary Layer. In order to examine transient flow phenomena, two turbulence conditions of nominally the same longitudinal integral length scale (Lxx/c?=?1) but with significantly different intensities (Ti?=?7.2?% and 12.3?%) were generated within a wind tunnel; time-varying surface pressure measurements, smoke flow visualization, and wake velocity measurements were made on a thin flat plate airfoil. Rapid changes in oncoming flow pitch angle resulted in the shear layer to separate from the leading edge of the airfoil even at lower geometric angles of attack. At higher geometric angles of attack, massive flow separation occurred at the leading edge followed by enhanced roll up of the shear layer. This lead to the formation of large Leading Edge Vortices (LEVs) that advected at a rate much lower than the mean flow speed while imparting high pressure fluctuations over the airfoil. The rate of LEV formation was dependent on the angle of attack until 10° and it was independent of the turbulence properties tested. The fluctuations in surface pressures and consequently aerodynamic loads were considerably limited on the airfoil bottom surface due to the favorable pressure gradient.