Asymmetric hydrogenation of 2-substituted N-protected-indoles catalyzed by rhodium complexes of BINOL-derived phosphoramidites

The rhodium-catalyzed asymmetric hydrogenation of 2-substituted N-protected-indoles using monodentate phosphoramidites as ligands was examined. Full conversion and 74% ee, were obtained with a catalyst based on PipPhos. The use of a catalytic amount of base is necessary for activity; best results were obtained with Cs₂CO₃.     

Overgroups of irreducible linear groups, II

Determining the subgroup structure of algebraic groups (over an algebraically closed field of arbitrary characteristic) often requires an understanding of those instances when a group and a closed subgroup both act irreducibly on some module , which is rational for and . In this paper and in Overgroups of irreducible linear groups, I (J. Algebra 181 (1996), 26-69), we give a classification of all such triples when is a non-connected algebraic group with simple identity component , is an irreducible -module with restricted -high weight(s), and is a simple algebraic group of classical type over sitting strictly between and .

     

Modeling the effect of suppression on the periodicity of stimulus frequency otoacoustic emissions

The distributed roughness theory of the origins of spectral periodicity in stimulus frequency otoacoustic emissions (SFOAEs) predicts that the spectral period will be altered by suppression of the traveling wave (TW) [Zweig and Shera, J. Acoust. Soc. Am. 98, 2018-2047 (1995)]. In order to investigate this effect in more detail, simulations of the variation of the spectral period under conditions of self-suppression and two-tone suppression are obtained from nonlinear cochlear models based on this theory. The results show that during self-suppression the spectral period is increased, while during high-side two-tone suppression, the period is reduced, indicating that the detailed pattern of disruption of the cochlear amplifier must be examined if the nonlinear behavior of SFOAEs is to be understood. The model results suggest that the SFOAE spectral period may be sensitive to changes in the state of the cochlear amplifier. A companion paper [Lineton and Lutman, J. Acoust. Soc. Am. 114, 871-882 (2003)] presents experimental data which are compared with the results of the above models with a view to testing the underlying theory of Zweig and Shera.     

A parametric model of the spectral periodicity of stimulus frequency otoacoustic emissions

A model for estimating the spectral period of stimulus frequency otoacoustic emissions (SFOAEs) is presented. The model characterizes the frequency spectrum of an SFOAE in terms of four parameters which can be directly related to cochlear mechanical quantities featuring in the theory of SFOAE generation proposed by Zweig and Shera [J. Acoust. Soc. Am. 98, 2018-2047 (1995)]. The results of applying the parametric model to SFOAEs generated by cochlear models suggest that it gives a sensitive measure of spectral period. It is concluded that the parametric model may be a useful tool for detecting small changes in cochlear function using SFOAE measurements.     

Improving conversion and enantioselectivity in hydrogenation by combining different monodentate phosphoramidites; a new combinatorial approach in asymmetric catalysis

The combination of monodentate ligands in the rhodium-catalysed enantioselective hydrogenation enables a new approach when searching for the optimal activity and enantioselectivity in catalysis.     

Chemistry of epoxysulfones: straightforward synthesis of versatile chiral building blocks

[reaction: see text] Several chiral building blocks have been obtained easily in large quantities from an epoxysulfone (9) that could be obtained in both enantiomeric forms from accessible starting materials.     

Application of monodentate secondary phosphine oxides,a new class of chiral ligands,in Ir(i)-catalyzed asymmetric imine hydrogenation

Secondary phosphine oxides were prepared from R(1)PCl(2) and R(2)MgBr, followed by hydrolysis. They were obtained in an enantiopure form by preparative chiral HPLC. These new monodentate ligands were tested in the iridium-catalyzed hydrogenation of imines at 25 bar. Enantioselectivities up to 76% were obtained at L/Ir = 2. Addition of pyridine (Pyr/Ir = 1:2) raised the ee to 83%. Using pyridine as an additive allowed reduction of the L/Ir ratio to 1 without reduction of ee. [reaction: see text]     

Mono- versus bidentate ligands in rhodium-catalyzed asymmetric hydrogenation. A comparative rate study

[reaction: see text] Bidentate chiral phosphines are no longer essential for achieving a fast and highly enantioselective hydrogenation of alpha- or beta-dehydroamino acid derivatives. In particular, a readily accessible and stable monodentate phosphoramidite can be highly effective in these asymmetric hydrogenations.     

Photochemical and thermal isomerization processes of a chiral auxiliary based donor-acceptor substituted chiroptical molecular switch: convergent synthesis,improved resolution and switching properties

A new type of chiroptical molecular switch is presented where irradiation employing different wavelengths of light induces a reversible helix inversion of a sterically overcrowded alkene bearing a second chiral entity in the form of a stereogenic center present in a pyrrolidine unit. The additional stereogenic center in the chiral auxiliary group has a distinct influence on the switching selectivity of this system and greatly facilitates the resolution of the different diastereoisomers, which is a considerable improvement compared with previously reported systems. In addition, the pyrrolidine stereogenic center causes small energetic differences between the various states of the switch system resulting in a small but significant directional preference in the helix inversion steps.