: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

The preparation, structure, and chemistry of hypervalent iodine compounds are reviewed with emphasis on their synthetic application. Compounds of iodine possess reactivity similar to that of transition metals, but have the advantage of environmental sustainability and efficient utilization of natural resources. These compounds are widely used in organic synthesis as selective oxidants and environmentally friendly reagents. Synthetic uses of hypervalent iodine reagents in halogenation reactions, various oxidations, rearrangements, aminations, C–C bond-forming reactions, and transition metal-catalyzed reactions are summarized and discussed. Recent discovery of hypervalent catalytic systems and recyclable reagents, and the development of new enantioselective reactions using chiral hypervalent iodine compounds represent a particularly important achievement in the field of hypervalent iodine chemistry. One of the goals of this Review is to attract the attention of the scientific community as to the benefits of...

Advances in Synthetic Applications of Hypervalent Iodine Compounds

Occurrence, Biogenesis, and Synthesis of Biologically Active Carbazole Alkaloids

Catalytic C-C bond-forming multi-component cascade or domino reactions: pushing the boundaries of complexity in asymmetric organocatalysis.

Asymmetric Organocatalytic Cyclization and Cycloaddition Reactions

The Wieland-MiescherKetone: A Journey from Organocatalysis to Natural Product Synthesis

The first total synthesis of anominine has been achieved, and the absolute configuration of the product has been determined. The key features include the development of a new, highly efficient organocatalyzed method for the asymmetric synthesis of Wieland-Miescher ketone building blocks, an unusual selenoxide [2,3]-sigmatropic rearrangement, and a ZrCl(4)-catalyzed indole coupling as well as several chemoselective transformations controlled by the structurally congested nature of the bicyclic core.

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Total synthesis of (-)-anominine.

This research was supported by the Ministerio de Ciencia e Innovacion (Spain)-FEDER through projects CTQ2007-
61338/BQU, CTQ2007-62771/BQU and Consolider Ingenio 2010 CSD2007-00006. Thanks are also due to the Comissionat per a Universitats i Recerca (Catalonia) for Grant 2005SGR-00442, Generalitat Valenciana for Grant (GVPRE/
2008/006) and the University of Alicante (GRJ06-05).

Efficient Solvent-Free Robinson Annulation Protocols for the Highly Enantioselective Synthesis of the Wieland–Miescher Ketone and Analogues

cis-Decahydroquinolines via asymmetric organocatalysis: application to the total synthesis of lycoposerramine Z.

An unprecedented C-C coupling reaction between alkenes and ketones by hydrogen-atom transfer, using Fe(acac)3 and PhSiH3 in EtOH, is described. This mild protocol features high site selectivity and allows the construction of sterically congested structures containing tertiary alcohols and quaternary centers. The overall process introduces a novel strategic bond disconnection for ring-closing reactions.

Ben Bradshaw

Papers

The Wieland-MiescherKetone: A Journey from Organocatalysis to Natural Product Synthesis

Total synthesis of (-)-anominine.

Efficient Solvent-Free Robinson Annulation Protocols for the Highly Enantioselective Synthesis of the Wieland–Miescher Ketone and Analogues

cis-Decahydroquinolines via asymmetric organocatalysis: application to the total synthesis of lycoposerramine Z.

Radical Cyclization of Alkene-Tethered Ketones Initiated by Hydrogen-Atom Transfer.