Palladium-Catalyzed Arylation of Endocyclic 1-Azaallyl Anions: Concise Synthesis of Unprotected Enantioenriched cis-2,3-Diarylpiperidines

Unprotected cis-2,3-diarylpiperidines are synthesized through an unprecedented palladium-catalyzed cross-coupling reaction between aryl halides and elusive endocyclic 1-azaallyl anions. These intermediates are generated in situ by the deprotonation of 2-aryl-1-piperideines, precursors that are readily prepared in two operations from simple piperidines. An asymmetric version of this reaction with (2R, 3R)-iPr-BI-DIME as the ligand provides products in moderate to good yields and enantioselectivities. This study significantly expands the synthetic utility of endocyclic 1-azaallyl anions.     

Structures of Azomethine Imines of the Pyrazolidone-(3)-type (I). The Structure of 1-(4-Nitrobenzylidene-pyrazolidone-(3)-betaine

1-(4-Nitrobenzylidene)-pyrazolidone-(3)-betaine crystallizes in the orthorhombic space group Pbca with eight molecules per unit cell. The lattice parameters are a = 11.025 Å; b = 22.995 Å; c = 7. 677 Å. With X-ray diffraction data, collected on a automatical four circle diffractometer, the crystal structure was solved by direct methods and refined to an R-value of 0.047 for 1516 symmetrically independent reflections. The structure determination has been performed to contribute to the explanation of the photochromic behaviour of this special class of azomethine imines.     

α-substituted Phosphoryl Compounds (I). The Crystal and Molecular Structure of Diethyl[5,6-dichloro-1,3-benzodioxol-(2)]-phosphonate,C11H13O5PCl2

Diethyl[5,6-dichloro- 1,3-benzodioxol-(2)]-phosphonate crystallizes in the triclinic space group P l̄ with two molecules per unit cell. The lattice parameters are a = 11.716 Å, b = 8.471 Å, c = 7.644 Å; α = 82.47° β = 95.81°, γ = 95.89°. With X-ray diffraction data collected on an automatic four circle diffractometer, the crystal structure was solved by direct methods and refined by least squares methods to an R value of 0.12 for 2374 measured reflections. The crystal used was im perfect. The substance is a derivative of acetales of formyl phosphoneacid esters. The aim is to find a correlation between the geometry of the structure and NMR data.     

ChemInform Abstract: The Gallides SrRh2Ga2, SrIr2Ga2, and Sr3Ir4Ga4.

The title gallides are prepared from the elements by induction melting and subsequent annealing (Ta ampules, 800 mbar Ar, 873—1073 K, 4 d) and characterized by powder and single crystal XRD.