RESUMO
Catalytic nitrite was found to enable carbon-oxygen bond-forming reductive elimination from unstable alkyl palladium intermediates, providing dioxygenated products from alkenes. A variety of functional groups were tolerated, and high yields (up to 94 %) were observed with many substrates, also for a multigram-scale reaction. Nitrogen dioxide, which could form from nitrite under the reaction conditions, was demonstrated to be a potential intermediate in the catalytic cycle. Furthermore, the reductive elimination event was probed with (18) O-labeling experiments, which demonstrated that both oxygen atoms in the difunctionalized products were derived from one molecule of acetic acid.
Assuntos
Alcenos/química , Nitritos/química , Paládio/química , Catálise , Oxirredução , Oxigênio/químicaRESUMO
A regio-, diastereo-, and enantioselective [4+3] cycloaddition between vinylcarbenes and dienes has been achieved using the dirhodium tetracarboxylate catalyst [Rh2(S-BTPCP)4]. This methodology provides facile access to 1,4-cycloheptadienes that are regioisomers of those formed from the tandem cyclopropanation/Cope rearrangement reaction of vinylcarbenes with dienes.
Assuntos
Acetatos/química , Alcadienos/química , Ródio/química , Catálise , Reação de Cicloadição , Estrutura Molecular , EstereoisomerismoRESUMO
The mol-ecular structure of 5,5'-bis(-hydroxy-methyl)-3,3'-biisoxazole, C8H8N2O4 (1), is composed of two trans planar isoxazole rings [r.m.s deviation = 0.006â (1)â Å], each connected with a methyl hydroxyl group. Similarly, the structure of 4,4',5,5'-tetrakis-(hydroxy-methyl)-3,3'-biisoxazole, C10H12N2O6 (2), is composed of two planar isoxazole rings [r.m.s. deviation = 0.002â (1)â Å], but with four hydroxymethyl groups as substituents. Both mol-ecules sit on a center of inversion, thus Z' = 0.5. The crystal structures are stabilized by networks of O-Hâ¯N [for (1)] and O-Hâ¯O hydrogen-bonding inter-actions [for (2)], giving rise to corrugated supra-molecular planes. The isoxazole rings are packed in a slip-stacked fashion, with centroid-to-centroid distances of 4.0652â (1)â Å for (1) (along the b-axis direction) and of 4.5379 (Å) for (2) (along the a-axis direction).
RESUMO
The mol-ecular structure of the title energetic compound, C8H6N4O8, is composed of two planar isoxazole rings and two near planar alkyl-nitrate groups (r.m.s deviation = 0.006â Å). In the crystal, the mol-ecule sits on an inversion center, thus Z' = 0.5. The dihedral angle between the isoxazole ring and the nitrate group is 69.58â (8)°. van der Waals contacts dominate the inter-molecular inter-actions. Inversion-related rings are in close slip-stacked proximity, with an inter-planar separation of 3.101â (3)â Å [centroid-centroid distance = 3.701â (3)â Å]. The measured and calculated densities are in good agreement (1.585 versus 1.610â Mgâ m-3).
RESUMO
The efficient and scalable synthesis of 3,3'-bis-isoxazole-5,5'-bis-methylene dinitrate and its energetic properties are described. The material has favorable sensitivity properties; energetic properties point toward its potential as both a melt-castable secondary explosive and as a propellant plasticizer.