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.     

High-power and high-temperature THz quantum-cascade lasers based on lens-coupled metal-metal waveguides

A metal-metal waveguide quantum cascade laser with an abutted silicon hyperhemispherical lens is demonstrated at ~4.1 THz. The device produced 145 mW of peak pulsed power at 5 K with a wall-plug power efficiency of 0.7%, lasing up to a maximum operating temperature of 160 K. The far-field beam pattern has a full width at half-maximum value of ~4.8 degrees in the H plane. The same device produced ~26 mW of peak power using a Winston cone instead of a lens, lasing up to 165 K. The large increase in output power is mainly attributed to an increase in collection efficiency.     

New class of magnetoresistance oscillations: interaction of a two-dimensional electron gas with leaky interface phonons

We report on a new class of magnetoresistance oscillations observed in a high-mobility two-dimensional electron gas (2DEG) in GaAs-Al(x)Ga(1--x)As heterostructures. Appearing in a weak magnetic field ( B < 0.3 T) and only in a narrow temperature range ( 2 K < T < 9 K), these oscillations are periodic in 1/B with a frequency proportional to the electron Fermi wave vector, k(F). We interpret the effect as a magnetophonon resonance of the 2DEG with leaky interface-acoustic phonon modes carrying a wave vector q = 2k(F). Calculations show a few branches of such modes existing on the GaAs-Al(x)Ga(1--)xAs interface, and their velocities are in quantitative agreement with the observation.