Regional Susceptibility in VCD Spectra to Dynamic Molecular Motions: The Case of a Benzyl α-Hydroxysilane.

Experimental and theoretical studies of the vibrational circular dichroism (VCD) spectrum of 3-methyl-1-(methyldiphenlsilyl)-1-phenylbutan-1-ol, whose absolute configuration is key to elucidating the Brook rearrangement of tertiary benzylic α-hydroxylsilanes, are presented. It is found that the entire OH-bending region in this spectrum-a region that provides important marker bands-cannot be reproduced at all by standard theoretical approaches even though other regions are well described. Using a novel approach to disentangle contributions to the rotational strength of these bands, internal coordinates are identified that critically influence the appearance of this part of the spectrum.

Lewis Acid Enabled Copper-Catalyzed Asymmetric Synthesis of Chiral β-Substituted Amides.

Here we report that readily available silyl- and boron-based Lewis acids in combination with chiral copper catalysts are able to overcome the reactivity issues of unactivated enamides, known as the least reactive carboxylic acid derivatives, toward alkylation with organomagnesium reagents. Allowing unequaled chemo-reactivity and stereocontrol in catalytic asymmetric conjugate addition to enamides, the method is distinguished by its unprecedented reaction scope, allowing even the most challenging and synthetically important methylations to be accomplished with good yields and excellent enantioselectivities. This catalytic protocol tolerates a broad temperature range (-78 °C to ambient) and scale up (10 g), while the chiral catalyst can be reused without affecting overall efficiency.

Copper-Catalyzed Enantioselective Alkylation of Enolizable Ketimines with Organomagnesium Reagents.

Inexpensive and readily available organomagnesium reagents were used for the catalytic enantioselective alkylation of enolizable N-sulfonyl ketimines. The low reactivity and competing enolization of the ketimines was overcome by the use of a copper-phosphine chiral catalyst, which also rendered the transformation highly chemoselective and enantioselective for a broad range of ketimine substrates.

Catalytic enantioselective addition of Grignard reagents to aromatic silyl ketimines.

α-Chiral amines are of significant importance in medicinal chemistry, asymmetric synthesis and material science, but methods for their efficient synthesis are scarce. In particular, the synthesis of α-chiral amines with the challenging tetrasubstituted carbon stereocentre is a long-standing problem and catalytic asymmetric additions of organometallic reagents to ketimines that would give direct access to these molecules are underdeveloped. Here we report a highly enantioselective catalytic synthesis of N-sulfonyl protected α-chiral silyl amines via the addition of inexpensive, easy to handle and readily available Grignard reagents to silyl ketimines.

Microwave-assisted solvent-free synthesis of enantiomerically pure N-(tert-butylsulfinyl)imines.

A simple, environmentally friendly, and very efficient procedure for the synthesis of optically pure N-(tert-butylsulfinyl)imines has been developed with microwave-promoted condensation of aldehydes and ketones using (R)-2-methylpropane-2-sulfinamide in the presence of Ti(OEt)(4), under solvent-free conditions. This procedure allows for the preparation of a variety of sulfinyl aldimines with excellent yields and purities in only 10 min, making any further purification of the imines unnecessary. Several sulfinyl ketimines have also been prepared in good yields by extension of the reaction times to 1 h.