Additions of enantiopure alpha-sulfinyl carbanions to (S)-N-sulfinimines: asymmetric synthesis of beta-amino sulfoxides and beta-alphamino alcohols

The addition of the lithium anions derived from (R)- and (S)-methyl and -ethyl p-tolyl sulfoxides to (S)-N-benzylidene-p-toluenesulfinamide provides an easy access route to enantiomerically pure beta-(N-sulfinyl)amino sulfoxides. Stereoselectivity can be achieved when the configurations at the sulfur atoms of the two reagents are opposite (matched pair), thus resulting in only one diastereoisomer, even for the case in which two new chiral centers are created. The N-sulfinyl group primarily controls the configuration of the carbon bonded to the nitrogen, whereas the configuration of the alpha-sulfinyl carbanion seems to be responsible for the level of asymmetric induction, as well as for the configuration of the new stereogenic C-SO carbon in the reactions with ethyl p-tolyl sulfoxides. An efficient method for transforming the obtained beta-(N-sulfinyl)amino sulfoxides into optically pure beta-amino alcohols, based on the stereoselective non-oxidative Pummerer reaction, is also reported.     

(Z)-3-p-tolylsulfinylacrylonitrile as a chiral dienophile: diels-alder reactions with furan and acyclic dienes

The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles.     

Spin-singlet clusters in the ladder compound NaV2O5

The space group of alpha(')-NaV2O5 turns below T(c) = 34 K from Pmmn with all V sites equivalent, into Fmm2 with three independent vanadium sites per layer. This is incompatible with models of charge ordering into V4+ and V5+. Our structure determination indicates that the phase transition consists of a charge ordering with three distinct valence states, formally V4+, V4.5+, and V5+. The singlet formation is not associated with dimerization on the spin ladder, but with the formation of spin clusters. Finally, we ascribe the quadrupling of the c axis to the large polarizability of the V2O5 skeleton.     

Dependence of pulser driving responses on electrical and motional characteristics of NDE ultrasonic probes

Acoustic performance in ultrasonic transmitters can be improved by means of a suitable electrical driving response and matching/tuning networks. It is important to predict this electrical response, but doing so is not easy because it departs notably from the nominal pattern with the loading probes. In practice, the analysis of HV pulser spikes in NDE applications requires fairly complex models in the transient regime and, in addition, non-linear problems could arise, especially in the case of tuned transmitters. In this paper, the most relevant influences of loading characteristics of NDT ultrasonic probes on the pulser electrical driving responses are evaluated in time and frequency domains. Conventional pulse generators and typical NDE pulsers are considered. Driving responses are analysed across commercial ultrasonic probes and, alternatively, across similar purely electrical loads. Distinct influences on pulser responses from electrical and motional sections of the probes are identified. All these aspects are studied on the basis of experimental and computer results.     

Measurement of the spin correlationA ookk innp elastic scattering between 0.63 and 1.08 GeV

We present the measurements of the spin correlation parameterA _ookk (np). A longitudinally polarized beam of free neutrons obtained from the break-up of polarized deuterons was scattered on the longitudinally polarized Saclay frozen-spin proton target. Measurements were carried out at SATURNE II, at neutron beam kinetic energies of 0.63, 0.88, 0.98 and 1.08 GeV. The data points cover the angular region from about 40° to 110° CM. The observed angular dependence ofA _ookk (np) at 0.63 GeV agree with the phase shift analysis predictions except at small angles.     

Total cross sections,elastic scattering observables and direct reconstruction of scattering matrix in np Interactions between 0.8 and 1.1 GeV at SATURNE II

Neutron-proton total cross section differences with the beam and target polarizations orientated either transversally or longitudinally with respect to the beam direction, as well as 11 spin dependent elastic scattering observables measured at SATURNE II as a function of energy and angle are presented. A major part of results was measured using the quasimonoenergetic polarized neutron beam and/or the polarized proton target. A small part of data was obtained using a polarized deuteron beam considered as a beam of quasifree neutrons and protons. The present paper represents a review of measured observables. Several sets of present data are compared with results obtained in other laboratories below 0.8 GeV. Imaginary parts of spin dependent forward amplitudes for np scattering and for the isospin stateI=0 were determined. First direct reconstruction of the np scattering matrix at 0.84 GeV is shown.We acknowledge support for this work from J. Arvieux, R. Beurtey, P. Borgeaud, P. A. Chamouard, A. Fleury, E. Heer, J. M. Laget, L. Musílek, L. Price, N. A. Russakovich, J. Saudinos, and J. Tolar. Discussions with J. Franz, J. M. Lagniel, C. Lechanoine-Leluc, G. Milleret, I. Strakovsky, and Y. Terrien have solved several problems. The exploitation of the polarized target owes a lot to G. Guillier, Ph. Marlet and J. Mommejat. We thank T. Lambert, E. Perrin, J. Poupard and J. P. Richeux for their efficient help in preparation of the experiment and the SATURNE II crew for unusual accelerator operations. Finally, we express our gratitude to Françoise Haroutel, who efficiently helped overcome all administrative requirements concerning a large international colaboration. This work was partly supported by the Swiss National Science Foundation and by the US Department of Energy Contract No. W-31-109-ENG-38.     

Peroxo and alkylperoxidic molybdenum(VI) complexes as intermediates in the epoxidation of olefins by alkyl hydroperoxides

Novel oxoperoxomolybdenum(VI) complexes with the general formula MoO(O₂)L₂X₂ (III, L = DMF, HMPT) and MoO(O₂)Cl(ON)L(IV, ON) = pyridin-2-carboxylate (Pic), 8-hydroxyquinolinate (Quin) were prepared from the reaction of Ph₃COOH or H₂O₂ with the corresponding cis-dioxo complexes. In the reaction with Ph₃COOH both oxygen atoms of the peroxo moiety were found, by ¹⁸O labeling experiments, to come from the hydroperoxide. The X-ray crystal structure of MoO(O₂)Cl(Pic)(HMPT) revealed a bipyramidal pentagonal surounding with a rather short OO distance (1.41 Å). Complexes III were found to be more reactive than MoO(O₂)₂,HMPT for the epoxidation of olefins (oxidative cleavage products are consecutively formed) but react by the same cyclic peroxymetalation mechanism. The absence of reaction in the case of complexes IV illustrates the necessity for the metal to possess an equatorial releasable coordination site adjacent to the peroxo group for the oxygen transfer to occur. Catalytic oxidation of olefins using Ph₃COOH gave a selectivity in oxygenated products very different from that using t-BuOOH, and ¹⁸O labeling studies showed that alkyl-peroxidic rather than peroxo species are intermediates in this latter reaction. The mechanism of epoxidation of olefins by alkyl hydroperoxides catalyzed by d⁰ metal complexes is discussed.     

Synthesis and Diels-Alder Reactions of a New Kind of Chiral Dienophiles: Cyclic Vinyl-p-tolylsulfilimines

A new kind of chiral dienophiles, cyclic vinyl-p-tolylsulfilimines (2a and 2b), were obtained from the corresponding (Z)-sulfinylacrylonitriles with HBF(4) and methanol. The asymmetric Diels-Alder reaction of optically pure 2a with cyclopentadiene under mild thermal or catalyzed conditions afforded only the endo-4a adduct with complete endo and pi-facial selectivities. The ability of the sulfilimine moiety to enhance the dienophilic reactivity of the double bond is similar to that of the sulfinyl group.