Reductive electrochemical formation of 6H-dibenzo[b,d]pyran-6-one and 2-benzopyran-1(1H)-one

In the present Letter several carbolactones (oxidative products) are obtained under aprotic cathodic conditions in the preparative scaled electrolysis of 1,2-quinones in a divided electrochemical cell and in the presence of oxygen. When 9,10-phenanthrenequinone is reduced 6H-dibenzo[b,d]pyran-6-one and [1,1′-biphenyl]-2,2′-dicarboxylic acid are obtained as major products. In the reduction of 1,2-naphthoquinone, 2-benzopyran-1(1H)-one, and 2-(2-carboxyethenyl)-benzoic acid were formed as main products. The proposed mechanism to explain the formation of these and other products, that involves an electron-transfer reaction to the oxygen in air, is now discussed.

A strongly magnetized pulsar within the grasp of the milky way’s supermassive black hole

The center of our Galaxy hosts a supermassive black hole, Sagittarius (Sgr) A∗. Young, massive stars within 0.5 pc of Sgr A∗ are evidence of an episode of intense star formation near the black hole a few million years ago, which might have left behind a young neutron star traveling deep into Sgr A∗’s gravitational potential. On 2013 April 25, a short X-ray burst was observed from the direction of the Galactic center. With a series of observations with the Chandra and the Swift satellites, we pinpoint the associated magnetar at an angular distance of 2.4±0.3 arcsec from Sgr A∗, and refine the source spin period and its derivative (P = 3.7635537(2) s and ˙ P = 6.61(4) × 10−12 s s−1), confirmed by quasi simultaneous radio observations performed with the Green Bank Telescope and Parkes Radio Telescope, which also constrain a dispersion measure of DM = 1750 ± 50 pc cm−3, the highest ever observed for a radio pulsar. We have found that this X-ray source is a young magnetar at ≈0.07–2 pc from Sgr A∗. Simulations of its possible motion around Sgr A∗ show that it is likely (∼90% probability) in a bound orbit around the black hole. The radiation front produced by the past activity from the magnetar passing through the molecular clouds surrounding the Galactic center region might be responsible for a large fraction of the light echoes observed in the Fe fluorescence features.

Synthesis of Chromen[4,3-b]pyrrolidines by Intramolecular 1,3-Dipolar Cycloadditions of Azomethine Ylides: An Experimental and Computational Assessment of the Origin of Stereocontrol

Azomethine ylides, generated from imine-derived O-cinnamyl or O-crotonyl salicylaldeyde and α-amino acids, undergo intramolecular 1,3-dipolar cycloaddition, leading to chromene[4,3-b]pyrrolidines. Two reaction conditions are used: (a) microwave-assisted heating (200 W, 185 °C) of a neat mixture of reagents, and (b) conventional heating (170 °C) in PEG-400 as solvent. In both cases, a mixture of two epimers at the α-position of the nitrogen atom in the pyrrolidine nucleus was formed through the less energetic endo-approach (B/C ring fusion). In many cases, the formation of the stereoisomer bearing a trans-arrangement into the B/C ring fusion was observed in high proportions. Comprehensive computational and kinetic simulation studies are detailed. An analysis of the stability of transient 1,3-dipoles, followed by an assessment of the intramolecular pathways and kinetics are also reported.