Organocatalytic asymmetric alpha-oxidation and amination reactions of carbonyl compounds are highly useful synthetic methodologies, especially in generating chiral building blocks that previously have not been easily accessible by traditional methods. The concept is relatively new and therefore the list of new catalysts, oxidizing and aminating reagents, as well as new substrates, are expanding at an amazing rate. The scope of this review includes new reactions and catalysts, mechanistic aspects and synthetic applications of alpha-oxidation, hydroxylation, aminoxylation, amination, hydrazination, hydroxyamination and related alpha-heteroatom functionalization of aldehydes, ketones and related active methylene compounds published during 2005-2009.
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http://dx.doi.org/10.3390/molecules15020917 | DOI Listing |
Chem Asian J
February 2023
College of Chemistry and Materials Science, Sichuan Normal University, Chengdu, 610068, China.
The synthetic methodologies for the α-functionalization of free carboxylic acids through the enediolate intermediates are summarized in this review. In general, the enediolates could be generated in situ or transiently from free carboxylic acids with a stoichiometric or catalytic amount of protection reagents, including metal, boron, and silicon reagents. The in situ or transient generated enediolates were subsequently subjected to racemic or asymmetric reactions with various electrophiles, producing the α-functionalized free carboxylic acids in a single step.
View Article and Find Full Text PDFACS Catal
November 2018
Department of Chemistry and Center for Integrated Biomolecular Communication, University of Nebraska-Lincoln, Lincoln, Nebraska 68588-0304, United States.
Phosphonate-directed catalytic asymmetric hydroboration (CAHB) of β-aryl/heteroaryl methylidenes and trisubstituted alkenes by pinacolborane enables facile access to functionalized, chiral tertiary benzylic boronic esters. Hydroboration is catalyzed by a chiral rhodium catalyst prepared from a Rh(I)-precursor in combination with a simple TADDOL-derived chiral cyclic monophosphite in a 1:1 ratio. The regio- and stereochemistry arises from the combined effects of the relative disposition of the directing group to the alkene, the alkene substitution pattern, and the necessity of an aryl substituent attached to the alkene.
View Article and Find Full Text PDFJ Am Chem Soc
February 2019
Department of Chemistry , University of North Carolina at Chapel Hill, Chapel Hill , North Carolina 27599-3290 , United States.
Feedstock aromatic compounds are compelling low-cost starting points from which molecular complexity can be generated rapidly via oxidative dearomatization. Oxidative dearomatizations commonly rely heavily on hypervalent iodine or heavy metals to provide the requisite thermodynamic driving force for overcoming aromatic stabilization energy. This article describes oxidative dearomatizations of 2-(hydroxymethyl)phenols via their derived bis(dichloroacetates) using hydrogen peroxide as a mild oxidant that intercepts a transient quinone methide.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2018
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470, Mülheim an der Ruhr, Germany.
The first direct and asymmetric α-aryloxylation of cyclic ketones via enol catalysis has been achieved using quinones as the reaction partners. Catalytic amounts of a phosphoric acid promote the exclusive formation of α,α-disubstituted ketones from the corresponding α-substituted ketones in good yields and enantioselectivities (up to 96.5:3.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2015
Department of Applied Biological Chemistry, Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657 (Japan).
An asymmetric formal synthesis of azadirachtin, a potent insect antifeedant, was accomplished in 30 steps to Ley's synthetic intermediate (longest linear sequence). The synthesis features: 1) rapid access to the optically active right-hand segment starting from the known 5-hydroxymethyl-2-cyclopentenone scaffold; 2) construction of the B and E rings by a key intramolecular tandem radical cyclization; 3) formation of the hemiacetal moiety in the C ring through the α-oxidation of the six-membered lactone followed by methanolysis.
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