Relativistic flying forcibly oscillating reflective diffraction grating.

Relativistic flying forcibly oscillating reflective diffraction gratings are formed by an intense laser pulse (driver) in plasma. The mirror surface is an electron density singularity near the joining area of the wake wave cavity and the bow wave; it moves together with the driver laser pulse and undergoes forced oscillations induced by the field. A counterpropagating weak laser pulse (source) is incident at grazing angles, being efficiently reflected and enriched by harmonics. The reflected spectrum consists of the source pulse base frequency and its harmonics, multiplied by a large factor due to the double Doppler effect.

Stereoselective synthesis of ß-hydroxy enamines, aminocyclopropanes, and 1,3-amino alcohols via asymmetric catalysis.

Tandem methods for the catalytic asymmetric preparation of enantioenriched ß-hydroxy (E)-enamines and aminocyclopropanes are presented. The diastereoselective hydrogenation of enantioenriched (E)-trisubstituted hydroxy enamines to generate 1,2-disubstituted-1,3-amino alcohols is also outlined. These methods are initiated by highly regioselective hydroboration of N-tosyl-substituted ynamides with diethylborane to generate ß-amino alkenyl boranes. In situ boron-to-zinc transmetalation generates ß-amino alkenylzinc reagents. These functionalized vinylzinc intermediates are subsequently added to aldehydes in the presence of a catalyst derived from an enantioenriched amino alcohol (morpholino isoborneol, MIB). The catalyst promotes highly enantioselective C-C bond formation to provide ß-hydroxy enamines in good isolated yields (68-86%) with 54-98% enantioselectivity. The intermediate zinc ß-alkoxy enamines can be subjected to a tandem cyclopropanation to afford aminocyclopropyl carbinols with three continuous stereocenters in a one-pot procedure with good yields (72-82%), enantioselectivities of 76-94%, and >20:1 diastereomeric ratios. Diastereoselective hydrogenation of isolated enantioenriched ß-hydroxy enamines over Pd/C furnished syn-1,2-disubstituted-1,3-amino alcohols in high yields (82-90%) with moderate to excellent diastereoselectivities. These methods were used in an efficient preparation of the enantioenriched precursor to PRC200-SS derivatives, which are potent serotonin-norepinephrine-dopamine reuptake inhibitors.

Simple one-pot conversion of aldehydes and ketones to enals.

A simple and efficient method to convert aldehydes into alpha,beta-unsaturated aldehydes with a two-carbon homologation is presented. Hydroboration of ethoxy acetylene with BH(3).SMe(2) generates tris(ethoxyvinyl) borane. Transmetalation with diethylzinc, addition to aldehydes or ketones, and acidic workup affords enals. When the addition is quenched with anilinium hydrochloride, 1,2-dithioglycol, or acetic anhydride, the unsaturated imine, dithiolane, or 1,1-diacetate is isolated in high yield. These transformations can be performed in a one-pot procedure.