Gram‐Scale Enantioselective Formal Synthesis of Morphine through an ortho–para Oxidative Phenolic Coupling Strategy

A gram‐scale catalytic enantioselective formal synthesis of morphine is described. The key steps of the synthesis involve an ortho–para oxidative phenolic coupling and a highly diastereoselective “desymmetrization” of the resulting cyclohexadienone that generates three of the four morphinan ring junction stereocenters in one step. The stereochemistry is controlled from a single carbinol center installed through catalytic enantioselective hydrogenation. These transformations enabled the preparation of large quantities of key intermediates and could support a practical and scalable synthesis of morphine and related derivatives.     

Hesseltin A, a novel antiviral metabolite from Penicillium hesseltinei

[structure: see text] Hesseltin A 1, a novel compound of mixed polyketide-terpenoid origins was isolated from the filamentous fungus Penicillium hesseltinei. The structure and stereochemistry were determined from extensive one- and two-dimensional NMR and mass spectral data.     

Laser-driven vehicles – from inner-space to outer-space

Laser-supported propulsion of a micro-airplane with a water-covered ablator is demonstrated. The repetitive use of an overlay structure is experimentally demonstrated with a specially designed water supply. Various transparent overlays are investigated by the CIP-based hydrodynamic code and by experiments using a pendulum and using a semi-conductor load cell. A momentum-coupling efficiency of ∼10⁴ N s/MJ is achieved by water–exotic-target experiments, in agreement with the simulation code, which predicts a maximum efficiency of ∼10⁵ N s/MJ. The concept of laser-supported propulsion can also be used for driving a Mach 5 airplane in the stratosphere, a micro-ship inside the human body, and a robot in a nuclear power reactor accident, during which large numbers of neutrons make electronic devices useless. Received: 7 October 2002 / Accepted: 20 January 2003 / Published online: 28 May 2003 RID="*" ID="*"Corresponding author. Fax: +81-3/5734-2165, E-mail: yabe@mech.titech.ac.jp     

Combinatorial data analysis: Confirmatory comparisons between sets of matrices

The task of assessing the similarity of pattern between the entries of two square matrices has been discussed extensively over the last decade, as a unifying strategy for approaching a variety of seemingly disparate statistical problems. As typically defined, the comparison depends on a measure of matrix correspondence, usually a normalized cross-product measure of some form, that is evaluated for relative size by the use of a reference distribution constructed through an equally likely permutation hypothesis defined at the level of the objects corresponding to the rows and columns of the two matrices. The extreme generality provided by this very simple framework subsumes a variety of different statistical problems, ranging from the study of spatial autocorrelation for variables observed over a set of geographic locations, to the topics of analysis of variance, the measurement of rank correlation, and confirmation techniques concerned with various conjectures of combinatorial structure that might be posited for an empirically determined measure of relationship between pairs of a given set of objects. The comparison strategies extant always assume that both matrices are fixed, and in those cases where one of the matrices codifies a given theoretical structure to be evaluated according to a second, this assumption can lead to substantial arbitrariness in how matrix similarity might be indexed, and thus, in how the comparison is implemented. As developed in this paper, exactly the same principles appropriate for use in the fixed comparison context can be extended to include matrices constructed through optimally weighted linear combinations of other sets of matrices. This generalization provides one mechanism for developing comparison strategies that allow assessment against very broad classes of matrices, which in turn serve to represent very general conjectures of possible combinatorial structure. This paper reviews some of these extensions in detail, with a particular emphasis on categorical and ordered categorical variables and whether they may reflect an empirically generated measure of object relationship.