Development of a New Lewis Acid-Catalyzed [3,3]-Sigmatropic Rearrangement: The Allenoate-Claisen Rearrangement

A new Lewis acid-catalyzed Claisen rearrangement has been developed that allows the stereoselective construction of β-amino-α,β,ε,ζ-unsaturated-γ,δ-disubstituted esters from simple allylic amines and allenoate esters. This reaction, which is contingent upon the use of Lewis acid, can be conducted with a range of metal salts (Yb(OTf)_3, AlCl_3, Sn(OTf)_2, Cu(OTf)_2, MgBr_2·Et_2O, FeCl_3, Zn(OTf)2) with catalyst loadings as low as 5 mol %. This catalytic process provides access to a diverse range of β-amino-α,β,ε,ζ-unsaturated-γ,δ-disubstituted esters in high yield and with excellent levels of diastereoselectivity for a series of allyl pyrrolidines (R_1 = H, Me, i-Pr, Ph, NR_2 = pyrrolidine, piperidine, Nme_2; ≥81% yield, ≥94:6 syn:anti) and allenoate esters (R_2 = H, Me, i-Pr, Ph, allyl, NPht, Cl; ≥75% yield, ≥91:9 syn:anti). The capacity of this new Claisen rearrangement to provide catalytic access to elusive structural motifs has also been demonstrated in the stereospecific formation of quaternary carbon bearing frameworks arising from geranyl- and neryl pyrrolidine (≥93% yield, >98:2 dr)

High-efficiency GaAs concentrator space cells

High efficiency Al sub x Ga sub 1-x As/GaAs heteroface solar concentrator cells have been developed for space applications. The cells, which were grown using metalorganic chemical vapor deposition (MOCVD), have been fabricated in both the p-n and n-p configurations. Magnesium and zinc are used as the p-type dopants, and Se is used as the n-type dopant. The space cells, which are designed for use in a Cassegrainian concentrator operating at 100 suns, AMO, have a circular illuminated area 4 mm in diameter on a 5 mm by 5 mm cell. These cells have exhibited flash-tested efficiencies as high as 23.6 percent at 28 C and 21.6 percent at 80 C

On the locus formed by the maximum heights of projectile motion with air resistance

We present an analysis on the geometrical place formed by the set of maxima of the trajectories of a projectile launched in a media with linear drag. Such a place, the locus of apexes, is written in term of the Lambert $W$ function in polar coordinates, confirming the special role played by this function in the problem. In order to characterize the locus, a study of its curvature is presented in two parameterizations, in terms of the launch angle and in the polar one. The angles of maximum curvature are compared with other important angles in the projectile problem. As an addendum, we find that the synchronous curve in this problem is a circle as in the drag-free case.Comment: 7 pages, 6 color eps figures. Synchronous curve added. Typos and style corrected

Enantioselective Organo-Cascade Catalysis

A new strategy for organocatalysis based on the biochemical blueprints of biosynthesis has enabled a new laboratory approach to cascade catalysis. Imidazolidinone-based catalytic cycles, involving iminium and enamine activation, have been successfully combined to allow a large diversity of nucleophiles (furans, thiophenes, indoles, butenolides, hydride sources, tertiary amino lactone equivalents) and electrophiles (fluorinating and chlorinating reagents) to undergo sequential addition with a wide array of α,β-unsaturated aldehydes. These new cascade catalysis protocols allow the invention of enantioselective transformations that were previously unknown, including the asymmetric catalytic addition of the elements of HF across a trisubstituted olefin. Importantly, these domino catalysis protocols can be mediated by a single imidazolidinone catalyst or using cycle-specific amine catalysts. In the latter case, cascade catalysis pathways can be readily modulated to provide a required diastereo- and enantioselective outcome via the judicious selection of the enantiomeric series of the amine catalysts. A central benefit of combining multiple asymmetric organocatalytic events into one sequence is the intrinsic requirement for enantioenrichment in the second induction cycle, as demonstrated by the enantioselectivities obtained throughout this study (≥99% ee in all cases)

Is copyright blind to the visual?

This article argues that, with respect to the copyright protection of works of visual art, the general uneasiness that has always pervaded the relationship between copyright law and concepts of creativity produces three anomalous results. One of these is that copyright lacks much in the way of a central concept of 'visual art' and, to the extent that it embraces any concept of the 'visual', it is rooted in the rhetorical discourse of the Renaissance. This means that copyright is poorly equipped to deal with modern developments in the visual arts. Secondly, the pervasive effect of rhetorical discourse appears to have made it particularly difficult for copyright law to strike a meaningful balance between protecting creativity and permitting its use in further creative works. Thirdly, just when rhetorical discourse might have been useful in identifying the significance and materiality of the unique one-off work of visual art, copyright law chooses to ignore its implications

Repeat-length variation in a wheat cellulose synthase-like gene is associated with altered tiller number and stem cell wall composition

The tiller inhibition gene (tin) that reduces tillering in wheat (Triticum aestivum) is also associated with large spikes, increased grain weight, and thick leaves and stems. In this study, comparison of near-isogenic lines (NILs) revealed changes in stem morphology, cell wall composition, and stem strength. Microscopic analysis of stem cross-sections and chemical analysis of stem tissue indicated that cell walls in tin lines were thicker and more lignified than in free-tillering NILs. Increased lignification was associated with stronger stems in tin plants. A candidate gene for tin was identified through map-based cloning and was predicted to encode a cellulose synthase-like (Csl) protein with homology to members of the CslA clade. Dinucleotide repeat-length polymorphism in the 5′UTR region of the Csl gene was associated with tiller number in diverse wheat germplasm and linked to expression differences of Csl transcripts between NILs. We propose that regulation of Csl transcript and/or protein levels affects carbon partitioning throughout the plant, which plays a key role in the tin phenotype.J. Hyles, S. Vautrin, F. Pettolino, C. MacMillan, Z. Stachurski, J. Breen, H. Berges, T. Wicker, and W. Spielmeye

Playing dice with mice: building experimental futures in Singapore

This is a postprint of an article published in New Genetics and Society, 2011, Vol. 30, Issue 4 pp. 433 – 441 © 2011 copyright Taylor & Francis. New Genetics and Society is available online at: http://www.tandfonline.com/loi/cngs20#.UqsI0tJdU24This short paper adds to debates on the unfolding spaces and logics of biotechnological development bought together in the 2009 special issue of New Genetics and Society on ‘Biopolitics in Asia’. Though an unlikely comparison between the development of the genomic sciences and the building of gambling casinos in the city state of Singapore, it reflects on the nature of political and technological investments in this South-East Asian city. It argues that Western expectations of a link between scientific practices, and civic epistemologies linked to democratic decision-making, are replaced by a rather different future orientation to scientific experimentation, economic investment and social development in Singapore

The Performance of Private Equity Funds: Does Diversification Matter?

This paper is the first systematic analysis of the impact of diversification on the performance of private equity funds. A unique data set allows the exact evaluation of diversification across the dimensions financing stages, industries, and countries. Very different levels of diversification can be observed across sample funds. While some funds are highly specialized others are highly diversified. The empirical results show that the rate of return of private equity funds declines with diversification across financing stages, but increases with diversification across industries. Accordingly, the fraction of portfolio companies which have a negative return or return nothing at all, increase with diversification across financing stages. Diversification across countries has no systematic effect on the performance of private equity funds