Heterofunctionalization catalysis with organometallic complexes of calcium, strontium and barium by...
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Transcript of Heterofunctionalization catalysis with organometallic complexes of calcium, strontium and barium by...
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