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.     

Ab initio study of AmCl(+): f-f spectroscopy and chemical binding

A valence full configuration interaction study with a polarized double-zeta quality basis set has been carried out for the lowest 49 electronic states of AmCl(+). The calculations use a pseudopotential treatment for the core electrons and incorporate a one-electron spin-orbit interaction operator. Electrons in the valence s, p, d, and f subshells were included in the active space. The resulting electronic potential energy curves are largely repulsive. The chemical bonding is ionic in character with negligible participation of 5f electrons. The molecular f-f spectroscopy of AmCl(+) arises essentially from an in situ Am(2+) core with states slightly redshifted by the presence of chloride ion. Am(+)+Cl asymptotes which give rise to the few attractive potential energy curves can be predicted by analysis of the f-f spectroscopy of isolated Am(+) and Am(2+). The attractive curves have substantial binding energies, on the order of 75-80 kcal/mol, and are noticeably lower than recent indirect measurements on the isovalent EuCl(+). An independent empirical correlation supports the predicted reduction in AmCl(+) binding energy. The energies of the repulsive curves are strongly dependent on the selection of the underlying atomic orbitals while the energies of the attractive curves do not display this sensitivity. The calculations were carried out using our recently developed parallel spin-orbit configuration interaction software.     

(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.     

Monotonicity properties of wholesale price contracts

This paper contributes to the supply chain contracts literature in economics and operations by performing qualitative sensitivity analysis of a wholesale price contract in a two-echelon supply chain setting. Order-theory tools are used to derive sufficient conditions for monotonicity of contract parameters.The upstream supplier is modeled as a Stackelberg leader. The supplier is assumed to have complete information about the costs and revenue function of the downstream retailer. It is shown that an equilibrium wholesale price weakly increases with an increase in the supplier production cost rate, but it may increase or decrease with an increase in the retailer cost rate. As either the supplier production cost or the retailer cost increases, the supplier profit decreases weakly. Additional sensitivity analysis is performed assuming certain properties of the retailer revenue function.Several well-known results in the supply chain contracting literature can be considered as special cases of the more general theorems developed here. In particular, this paper reexamines the analysis of a newsvendor supply chain problem by Lariviere and Porteus [Lariviere, M.A., Porteus, E.L., 2001. Selling to the newsvendor: An analysis of price-only contracts. Manufacturing & Service Operations Management 3, 293–305]. This paper generalizes and extends their work, by establishing properties of the newsvendor demand distribution that guarantee monotonicity of the contract parameters, without requiring a unique contract solution.     

On the complexity of project scheduling to minimize exposed time

We consider project scheduling where the project manager’s objective is to minimize the time from when an adversary discovers the project until the completion of the project. We analyze the complexity of the problem identifying both polynomially solvable and NP-hard versions of the problem. The complexity of the problem is seen to be dependent on the nature of renewable resource constraints, precedence constraints, and the ability to crash activities in the project.     

The intersection of free submonoids of a free monoid is free

Several necessary and sufficient conditions exist for a submonoid of a free monoid to be free. For a few, see [1] through [6]. This short note uses one of these conditions, due to Schützenberger (see [2], p. 119, or [4], Theorem 1.4) to establish that the intersection of free submonoids of a free monoid M is again free. Schützenberger's condition is also proven in this note.     

Decomposition and complexity of finite semigroups

The Prime Decomposition Theorem for finite transformation semigroups of Krohn and Rhodes and the resultant theory of complexity of finite semigroups are the subjects of this survey. All concepts used are defined in the text, and proofs are given if they are accessible without a large amount of preparation. This article is an attempt to lead the reader to the essential ideas of the theory in the shortest possible time and effort.