Symmetrical Distortion of the Methyl Group of Methyltrichlorotitanium: Gas Phase Structure and H,H Coupling Constant
Electron-diffraction studies show gaseous TiMeCl3 to have a symmetrically 'flattened' (C3v) methyl group with an H-C-Ti angle of 101.0+/-2.2 deg, which is reflected in solution by a most unusual large positive H,H coupling constant of +11.3 Hz; these data are interpreted in terms of a ?-donor interaction of methyl C-H bonds with low-lying metal d-orbitals.
Berry, Adam,Dawoodi, Zain,Derome, Andrew E.,Dickinson, J. Mark,Downs, Anthony J.,et al.
Development of a Synthesis of a 2,3-Disubstituted 4,7-Diazaindole Including Large-Scale Application of CH3Li/TiCl4-Mediated Methylation of an Enolizable Ketone
The chemical development of a 2,3-disubstituted 4,7-diazaindole is described. The requisite tertiary carbinol substrate was prepared employing in situ-generated CH3TiCl3 as a chemoselective and preferred reagent compared to CH3MgX for methyl addition to an enolizable ketone. The 4,7-diazaindole ring system was efficiently assembled via an intramolecular Chichibabin transformation. The optimized processes were performed on pilot-plant scale to provide kilogram quantities of the target molecule.
Weiberth, Franz J.,Gill, Harpal S.,Lee, George E.,Ngo, Duc P.,Shrimp, Frederick L.,Chen, Xuemin,D'Netto, Geoffrey,Jackson, Bryan R.,Jiang, Ying,Kumar, Narendra,Roberts, Frederick,Zlotnikov, Evgeny
p. 806 - 811
(2015/07/27)
2 -ARYLAMINOQUINAZOLINES FOR TREATING PROLIFERATIVE DISEASES
The invention provides novel compounds that are inhibitors of PDKI. Also provided are pharmaceutical compositions including the compounds, and methods of treating proliferative diseases, such as cancers, with the compounds or composition.
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Page/Page column 185-186
(2010/01/12)
Evidence for Carbon-Hydrogen-Titanium Interactions: Synthesis and Crystal Stuctures of the Agostic Alkyls (R=Et or Me)
The compounds (R=Me, CH2D, or Et; dmpe=Me2PCH2CH2PMe2) have been prepared.An X-ray crystal structure determination of shows that the Ti-C-C angle of the Ti-Et moiety is 86.3(6) deg.Variable-temperature n.m.r. studies show the molecule to be fluxional at room temperature.At -90 deg C the n.m.r. spectra correspond to the structure found in the crystal and J(C-H) for the ethyl CH2 hydrogens is 150.2 Hz.It is concluded that the ethyl group is bonded by a system.The crystal structure of has been determined from X-ray and neutron diffraction data.The data show the methyl group to be distorted such that it is tilted with respect to the Ti-C vector and one hydrogen atom closely approaches the Ti centre giving an angle for Ti-C-H of 93.5(2) deg. (neutron data).Variable-temperature n.m.r. studies show that (R=CH3 or CH2D) are fluxional but provide no evidence for differentiation of the C-H moiety of the methyl group.
Dawoodi, Zain,Green, Malcolm L.H.,Mtetwa, Victor S. B.,Prout, Keith,Schultz, Arthur J.,et al.
p. 1629 - 1638
(2007/10/02)
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