A kinetic resolution of racemic 2-substituted
cyclopentanones via
highly regio- and enantioselective Baeyer–Villiger oxidation
has been successfully developed. The reaction could afford the normal
6-substituted δ-lactones in up to 98% ee and >19/1 regioselectivity.
Meanwhile, the unreacted ketones were recovered in excellent ee values
(up to 98%). It represents the best results of the kinetic resolution
of racemic 2-substituted cyclopentanones via nonenzymic asymmetric
BV oxidation.
A catalytic regio-
and enantioselective haloazidation reaction
with a chiral iron(II) complex catalyst under mild reaction conditions
was reported. By this approach, the stereoselective α-halo-β-azido
difunctionalization of both α,β-unsaturated amides and
α,β-unsaturated esters was achieved. This method enabled
the construction of a broad spectrum of valuable functionalized amides
and esters, including enantiomerically enriched β-azido amides,
aziridine amides, α-amino amide derivatives, β-triazole
amides, functionalized peptide derivatives, and α-halo-β-azido-substituted
esters.
Ah ighly efficientc hiral N,N'-dioxidezinc(II) complexc atalytic system hasb een developed for the enantioselective aza-Friedel-Crafts reaction of isatin-derived ketimines with indoles. A series of enantiomerically enriched 3-indolyl-3-aminooxindoles containing at etrasubstituted stereocenter were obtained in up to 99% yield with up to 96% ee.F urthermore,c ontrol experiments provide afundamental sight into the mechanism of the reaction.
Classical kinetic resolution, parallel kinetic resolution and desymmetrization were achieved by asymmetric BV oxidation of 3-substituted and meso-disubstituted cycloketones.
An efficient diastereo- and enantioselective [3 + 2] cycloaddition of heterosubstituted alkenes with oxiranes via selective C-C bond cleavage of epoxides has been developed. The reaction was catalyzed by a chiral N,N'-dioxide/Ni(II) catalyst, and a variety of chiral highly substituted tetrahydrofurans were obtained in up to 99% yield, 92/8 dr, and 99% ee.
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