A survey on the reactivity of phenyliodonium ylide of 2-hydroxy-1,4-naphthoquinone with amino compounds

The phenyliodonium ylide of 2-hydroxy-1,4-naphthoquinone reacts with aminoesters, ureas, aminoalcohols and aminophenols in refluxing dichloromethane to afford good yields of indanedione 2-carboxamido compounds, that in solution exist in an enol-amide form. The same reactants in a copper-catalyzed reaction afford mainly the corresponding N-arylo compounds. Arylhydrazines are mainly oxidized by the ylide and arylation occurs only in a low yield.     

Kinetic study of various phosphoramidite ligands in the iridium-catalyzed allylic substitution

[reaction: see text] A comparative kinetic study of seven ligands is presented which clearly shows that a slight difference in the substitution pattern of the aryl group on the amine moiety of the ligand dramatically alters the activity of the resulting iridium catalyst. Ligand L6 shows the most impressive kinetics as well as the highest enantioselectivities.     

A free-electron study of color vision

The primary process of vision, consisting of photochemical isomerization ofcis totrans retinal, occurs at three different wavelengths to enable color vision. According to current evidence the successive red shifts to higher wavelength absorption is due to the relative displacement of ions in the vicinity of the chromophore. Free-electron modeling of the absorption spectrum shows that a relative displacement of the counter-ion, associated with the quaternary nitrogen, by 0.5 Å is sufficient to cause the red shift needed to cover the entire spectrum.     

New large sets of t‐designs

Abstact: We introduce generalizations of earlier direct methods for constructing large sets of t‐designs. These are based on assembling systematically orbits of t‐homogeneous permutation groups in their induced actions on k‐subsets. By means of these techniques and the known recursive methods we construct an extensive number of new large sets, including new infinite families. In particular, a new series of LS[3](2(2 + m), 8·3^m ? 2, 16·3^m ? 3) is obtained. This also provides the smallest known ν for a t‐(ν, k, λ) design when t ≥ 16. We present our results compactly for ν ≤ 61, in tables derived from Pascal's triangle modulo appropriate primes. © 2000 John Wiley & Sons, Inc. J Combin Designs 9: 40–59, 2001     

Furanoside phosphite–phosphoroamidite and diphosphoroamidite ligands applied to asymmetric Cu-catalyzed allylic substitution reactions

A phosphite–phosphoroamidite and diphosphoroamidite ligand library was applied in the Cu-catalyzed allylic substitution of a range of cinnamyl-type substrates using several organometallic nucleophiles. Results indicated that selectivity depended strongly on the ligand parameters (position of the phosphoroamidite group at either C-5 or C-3 of the furanoside backbone, as well as the configuration of C-3, the introduction of a second phosphoroamidite moiety, the substituents and configurations in the biaryl phosphite/phosphoroamidite moieties), the nature of the leaving group of the substrate and the alkylating reagent. Good enantioselectivities (up to 76%) and activity combined with high regioselectivities were obtained.     

Reactions Between 4-Hydroxycoumarins or 4-Hydroxy-1-Methylquinolinone and Dmad in the Presence of Phosphites. Synthesis of (Chromen-3-YL)- and (Quinolin-3-YL)-(Dialkoxyphosphoryl)Succinates

Abstract

Dimethyl (chromen-3-yl)-(dialkoxyphosphoryl)succinates are prepared from the reaction of 4-hydroxycoumarin with DMAD and P(OR)₃. 4-Hydroxy-1-methylquinolinone reacts with DMAD and P(OEt)₃ to give dimethyl (quinoline-3-yl)-(diethoxyphosphoryl)-succinate.

GRAPHICAL ABSTRACT      

Enantio‐ and Regioselective Conjugate Addition of Organometallic Reagents to Linear Polyconjugated Nitroolefins

The copper‐catalysed conjugate addition of trialkylaluminium and dialkylzinc reagents to polyconjugated nitroolefins (nitrodiene and nitroenyne derivatives) is reported. A reversed Josiphos ligand L7 allows for the selective 1,4‐ or 1,6‐addition with high enantioselectivities.