A efficient two-step synthesis of symmetrical and unsymmetrical tetrahydrospiro-biquinolines from o-azidobenzaldehydes is reported. The previously unreported series of tetrahydrospiro-biquinolines wer accessed through sequential double aldol condensation with acetone, cyclopentanone and cyclohexanone to the corresponding o,oâ-diazido-dibenzylidene-acetone, -cyclopentanone and -cyclohexanone derivatives and hydrogenation-spirocyclization. Further elaboration of the spiro-diamines was demonstrated by electrophilic aromatic bromination, Suzuki coupling and N-alkylation, which all proceeded with preservation of the spirocyclic core.
293.7 K - TS and Reactant 298 K - TS, IRC, Reactant, Product G(d,p) - TS and Reactant Def2TZVPP - TS and Reactant
Tosyl Lactone (Q&R) [3,3]-sigmatropic rearrangement. Lactone conformational energies. Sulfoximines (X) [3,3]-sigmatropic rearrangement. Aliphatic tosyl acetate stereospecific [3,3]-sigmatropic rearrangement.
Chair transition states compounds: A, B, C, D, E, F, G, H, I, J, K, L, M. For activating groups, nitrile, pyridylsulfonyls, nitro and trifluoro methyl. Occasional boat TS is calculated, or using different solvents to DCM.
A few years back, I took a look at the valence-shell electron pair repulsion approach to the geometry of chlorine trifluoride, ClF3 using so-called ELF basins to locate centroids for both the covalent F-Cl bond electrons and the chlorine lone-pair electrons. Whereas the original VSEPR theory talks about five "electron pairs" totalling an octet-busting ten electrons surrounding chlorine, the electron density-based ELF approach located only ~6.8e surrounding the central chlorine and no "octet-busting". The remaining...
A series of fluoroolefins react with a monomeric Al(I) complex by oxidative addition. These reactions break either strong sp2 or sp3 CâF bonds and result in the formation of a diverse array of organoaluminium compounds which all contain three carbon atoms, but varying fluorine content, connectivity and stereochemistry. Preliminary mechanistic studies suggest that a minimum of two mechanisms may be in operation. The first is a direct oxidative addition of the CâF bond to Al(I)...
A mechanistic insight into the boron-catalysed direct amidation reaction. Computational data for one amine cycle + D3BJ Dispersion.Henry Rzepa
Computational data for catalytic cycles for amidation of a carboxylic acid using boron catalysts obtained using the Gaussian09, rev D.01 and E.01. The one amine cycle using the D3BJ dispersion correction
A mechanistic insight into the boron-catalysed direct amidation reaction. Phenyl substituents. Computational data for one amine cycle with additional amine forming B-N-B bridge to replace B-O-B bridge.Henry Rzepa
Gaussian 16 calculated free energies for mechanistic cycle.
NMR data and chemdraw files for compounds 1 - 5. .mnpub files are digitally signed file for use with MestreNova 11, containing a temporary license file which unlocks the full functionality of the MestreNova 11+ program for these specified dataset only. More information about mpublish project: 10.14469/hpc/1763 and 10.14469/hpc/1615
Reactivity studies of zinc-aryl complexes towards carbon dioxide, alcohols, epoxides and anhydrides are investigated using a combination of experimental methods and density functional theory calculations.
Crystal structure data for Synthesis and Reactions of Benzannulated Spiroaminals; TetrahydrospirobiquinolinesJoshua Almond-Thynne
X-Ray crystallographic data for compounds 14a, 18b, 19b,25, 26, 27 and 29. Including raw data collected by diffractometer.
The prenyl moiety is present in vast numbers of naturally occurring compounds. Many of these are commercially available and very cheap, therefore, if they can be incorporated as a building block for organic syntheses, they can add great value. Furthermore, the synthesis of more structurally complex natural products, particularly those with a terpenoid framework, may proceed via compounds that contain the prenyl grouping. A plethora of metathesis reactions are used in natural product synthesis, despite...
tpap, as it is affectionately known, is a ruthenium-based oxidant of primary alcohols to aldehydes discovered by Griffith and Ley. Whereas ruthenium tetroxide (RuO4) is a voracious oxidant, its radical anion countered by a tetra-propylammonium cation is considered a more moderate animal. In this post, I want to try to use quantum mechanically derived energies as a pathfinder for exploring what might be going on (or a reality-check if you like). The calculations are at...
I started this story by looking at octet expansion and hypervalence in non-polar hypercoordinate species such as SMe6, then moved to S(CH2)3. Finally now its the turn of HCâ¡Sâ¡CH.