Catalytic Asymmetric Transfer Hydrogenation of trans-Chalcone Derivatives Using BINOL-derived Boro-phosphates.

Chiral phosphoric-acid-catalyzed asymmetric reductions of trans-chalcones have been investigated in this work. A BINOL-derived boro-phosphate-catalyzed asymmetric transfer hydrogenation of the carbon-carbon double bond of trans-chalcone derivatives employing borane as a hydride source was realized. This methodology provides a convenient procedure to access chiral dihydrochalone derivatives in high yields and with high enantioselectivities under mild conditions.

Novel Hybrid Prins/Aza-Prins Oxocarbenium/N-Acyliminium Cascade: Expedient Access to Complex Indolizidines.

Heavy silyl enol ethers (mostly TIPS and TBS) combine with cyclic N-alkenyl N-acyliminium salts generated in situ from their N,O-acetal precursors, to furnish highly functionalized indolizidines through an unprecedented double Mukaiyama-Mannich-Prins cascade transformation. This novel cascade annulation process demonstrates a promising scope, and takes place mostly catalytically with interesting stereocontrol. Furthermore, an appealing facet of this chemistry is emphasized with a bicatalytic approach by which the Mannich-Prins cascade follows a Ru-catalyzed N-allylamide to N-(E)-propenyl isomerization of the aminal counterpart in a one-pot operation.

Access to alpha-substituted amino acid derivatives via 1,3-dipolar cycloaddition of alpha-amino ester derived nitrones.

Amino acid derived nitrones were conveniently synthesized in good-to-excellent yields by condensation of alpha-ketoesters with N-benzylhydroxylamine. The cycloaddition reactions of these nitrones with different alkenes were investigated under thermal solvent-free conditions. Considering conversions, yields, and selectivities, alkyl vinyl ethers have proven to be valuable partners to achieve this transformation, which creates a tetrafunctionalized stereogenic quaternary center. From the adducts derived from vinyl ethers, a three-step access to highly functionalized alpha-substituted amino acid derivatives is described.

B-Alkylcatecholborane-mediated tandem radical conjugated addition-aldol cyclization.

A one-pot procedure involving radical conjugate addition of B-alkylcatecholboranes to enones followed by intramolecular aldol reaction is reported. Application to the stereoselective synthesis of monocyclic and bicyclic products with up to four contiguous stereogenic centers is presented.