Post on 18-Dec-2015
Heterofunctionalization catalysis with organometallic complexes of calcium, strontium and barium
by Anthony G. M. Barrett, Mark R. Crimmin, Michael S. Hill, and Panayiotis A. Procopiou
Proceedings AVolume ():rspa20090558
January 25, 2010
©2010 by The Royal Society
(a) Fundamental reactions of trivalent lanthanide organometallics: (i) σ-bond metathesis and (ii) insertion of unsaturated substrates into M–X2 σ-bonds.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
The Schlenk equilibrium of heavier Group II complexes.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
Selected examples of well-defined, kinetically stabilized, heteroleptic heavier Group II complexes.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
Calcium-mediated stereocontrolled polymerization of rac-lactide.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
Reaction scope of calcium and magnesium mediated intramolecular hydroamination of aminoalkenes.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
Diastereoselectivity in the intramolecular hydroamination of pro-chiral aminoalkenes.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
(a) Reaction of pre-catalysts 1 and 2 with primary amines.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
Proposed mechanism of Group II mediated hydroamination of aminoalkenes with (a) non-reversible and (b) reversible pre-catalyst generation.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
Aminotroponate, aminotropiniminate, bis(imidazolin-2-ylidene-1-yl)borate, tris (imi- dazolin-2-ylidene-1-yl)borate and triazenide supported Group II pre-catalysts for intramolecular
hydroamination.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
Scope of hydroamination catalysis with complexes 3–9 and 11–12.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
Side-by-side comparison of reaction conditions for the intramolecular cyclization of 1-amino-2,2-diphenyl-4-pentene.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
Intermolecular hydroamination mediated by Group II complexes.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
Proposed transition states to C–N bond formation in the anti-Markovnikov hydroamination of styrenes.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
Free energy profiles for the reaction of ethylene with ammonia catalysed by [{HNC(Me)CHC(Me)NH}M(NH2)].
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
Electron density difference maps for the alkene insertion (a) transition state and (b) intermediate for the Mg-mediated cycle.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
Insertion of 1,3-dialkyl carbodiimides into the Ca–N bonds of derivatives of 1.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
Scope of Group II mediated hydroamination of carbodiimides.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
(a) Proposed mechanism of the Group II mediated hydroamination of carbodiimides and (b) ORTEP representation of 13 thermal ellipsoids at 40% probability; H atoms are omitted
for clarity.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
Group II catalysed addition of diphenylamine to isocyanates.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
(a) Proposed mechanism of the Group II catalysed addition of diphenylamine to isocyanates.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
Scope of alkene and alkyne hydrophosphination mediated by 1.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
Explanation for the observed regiochemistry in the Group II mediated hydrophos- phination of styrenes.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
(a) Proposed mechanism of the hydrophosphination of diphenylacetylene catalysed by 1 and (b) ORTEP representation of 15 thermal ellipsoids at 20% probability; H atoms are omitted for
clarity.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
Hydrophosphination of diphenylacetylene and 1,4-diphenylbutadiyne catalysed by [Ca{PPh2}2(THF)4].
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
Group II mediated hydrophosphination of carbodiimides.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
(a) Proposed mechanism of Group II mediated hydrophosphination of carbodiimides.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
Scope of Group II mediated hydrosilylation of alkenes and dienes.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
Reaction of 1 with PhSiH3 to yield the molecular hydride 17.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
Proposed mechanisms of the Group II mediated hydrosilylation of alkenes.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
Group II catalysed hydrosilylation of ketones.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society
Reaction scope of the calcium-mediated hydrogenation of activated alkenes.
Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558
©2010 by The Royal Society