Total Synthesis of C30 Botryococcene and epi‐Botryococcene by a Diastereoselective Ring Opening of Alkenylcyclopropanes

Trialkylaluminum compounds perform a diastereoselective 1,6‐ring fragmentation of alkenylcyclopropane. This new tool allows the preparation of hydrocarbon compounds containing two distant stereocenters with a good diastereocontrol. Inspired by the biosynthesis of botryococcene this methodology was applied successfully to the diastereo‐ and enantioselective preparation of this triterpene and its epimer.     

New One-Pot Synthesis of ò-Iodoalkyne

A high yielding, one-pot general procedure for the synthesis of ò-iodoalkyne is described.     

Regioselective carbon-carbon bond cleavage in the oxidation of cyclopropenylcarbinols

The strained double bond of cyclopropenylcarbinols undergoes a facile oxidation reaction to lead to unsaturated carbonyl derivatives. The distribution of the formed products depends on the relative stability of carbon-centered radical species, and the Sharpless kinetic resolution leads to enantiomerically pure Baylis-Hillman enal adducts.     

Stereoselective Access to Fully Substituted Aldehyde-Derived Silyl Enol Ethers by Iridium-Catalyzed Alkene Isomerization

An in situ generated cationic Ir-catalyst isomerizes simple allylic silyl ethers into valuable, fully substituted aldehyde-derived silyl enol ethers. Importantly, by judicious choice of substrate, either of the two possible stereoisomers of a given enolate derivative is accessible with complete stereoselectivity. One-pot isomerization-aldol and isomerization-allylation processes illustrate the synthetic utility of this method.     

Functions that have read‐twice constant width branching programs are not necessarily testable

We construct a property on 0/1‐strings that has a representation by a collection of width‐3 read‐twice oblivious branching programs, but for which any two‐sided ?‐testing algorithm must query at least Ω(n^δ) many queries for some fixed ? and δ. This shows that Newman's result [Testing of functions that have small width branching programs, SIAM J Comput 31 (2002), 1557–1570] cannot be generalized to read‐k‐times functions for k > 1. In addition, we exhibit a property that has also a representation by a CNF formula of constant clause size. Hence, the nontestability results extend to properties that in addition have small (constant size) 0‐witnesses. © 2004 Wiley Periodicals, Inc. Random Struct. Alg., 2004     

Experimental estimation of a D-shaped cylinder wake using body-mounted sensors

The effectiveness of a small array of body-mounted sensors, for estimation and eventually feedback flow control of a D-shaped cylinder wake is investigated experimentally. The research is aimed at suppressing unsteady loads resulting from the von-Kármán vortex shedding in the wake of bluff-bodies at a Reynolds number range of 100–1,000. A low-dimensional proper orthogonal decomposition (POD) procedure was applied to the stream-wise and cross-stream velocities in the near wake flow field, with steady-state vortex shedding, obtained using particle image velocimetry (PIV). Data were collected in the unforced condition, which served as a baseline, as well as during influence of forcing within the “lock-in” region. The design of sensor number and placement was based on data from a laminar direct numerical simulation of the Navier-Stokes equations. A linear stochastic estimator (LSE) was employed to map the surface-mounted hot-film sensor signals to the temporal coefficients of the reduced order model of the wake flow field in order to provide accurate yet compact estimates of the low-dimensional states. For a three-sensor configuration, results show that the estimation error of the first two cross-stream modes is within 20–40% of the PIV-generated POD time coefficients. Based on previous investigations, this level of error is acceptable for a moderately robust controller required for feedback flow control.     

Isoxazole‐Embedded Allylic Zinc Reagent for the Diastereoselective Preparation of Highly Functionalized Aldol‐Type Derivatives Bearing a Stereocontrolled Quaternary Center

Highly functionalized aldol‐type products bearing a β‐quaternary center and a stereoselectively controlled γ‐hydroxy function are readily prepared by the diastereoselective addition of an allylic zinc reagent embedded in an isoxazole ring to various aromatic and heteroaromatic aldehydes, in the presence of Lewis acids, such as MgCl₂ or LaCl₃?2 LiCl. After reductive cleavage of the N?O bond by using Fe, NH₄Cl, aldol‐type products bearing a stereocontrolled β‐quaternary center and a γ‐hydroxy group were observed. The benzylic reactivity of the isoxazolylmethylzinc reagent towards other electrophiles, such as acid chlorides, aryl and allylic halides, as well as aldehydes in the presence of BF₃?OEt₂ are also described.