The Acyloin Condensation

Bloomfield, Jordan J.; Owsley, Dennis C.; Nelke, Janice M.

doi:10.1002/0471264180.or023.02

Cited by 3 publications

(1 citation statement)

References 259 publications

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“…Indeed, whereas the term “benzoin condensation” unequivocally identifies the homocoupling of benzaldehydes to give benzoins, the term “acyloin condensation” is also used to indicate the synthesis of symmetrical α‐hydroxy ketones by reductive condensation of esters in the presence of sodium …”

Section: Introductionmentioning

confidence: 99%

Thiamine‐Diphosphate‐Dependent Enzymes as Catalytic Tools for the Asymmetric Benzoin‐Type Reaction

2016

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Benzoin-type reactions allow the generation of α- hydroxy ketones through the (formal) carboligation of two alde- hyde reactants. The synthetic relevance of the products and the wide distribution of the α-hydroxy ketone functionality in bioactive natural compounds have provided the motivation for intensive research efforts directed towards the development of ever more efficient and selective catalysts for reactions of this class. As in many other areas of study, the solution developed in nature – that is, the utilization of thiamine-diphosphate-dependent (ThDP-dependent) enzymes – also in this case allows levels of chemo- and stereoselectivity currently unattainable by biomimetic organocatalysts to be achieved. Here we present an overview of the structural diversity of the α-hydroxy ketone motif achievable through ThDP-dependent enzyme catalysis. Details relating to structure–activity relationships and to ra- tional mutagenesis approaches for improving the catalytic per- formances of wild-type enzymes are also illustrated

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Section: Introductionmentioning

confidence: 99%

Thiamine‐Diphosphate‐Dependent Enzymes as Catalytic Tools for the Asymmetric Benzoin‐Type Reaction

2016

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Macrocyclization Reactions at High Concentration (≥0.2M): The Role of Catalysis

Garnes-Portolés

Leyva‐Pérez

2023

ACS Catal.

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The synthesis of macrocycles is fundamental to obtain useful quantities of this unique family of organic compounds. However, most current syntheses still require highly diluted conditions (generally < 0.1M), which makes the synthesis extremely inefficient in the reactor volume. Here we review, quantify, and analyze the few synthetic methods for macrocycles reported so far where the reaction solution is at ≥ 0.2 M concentration. Parametrization of the results with the Emac (efficiency macrocyclization) index unveils that catalytic methods are much more efficient than non-catalyzed methods. Beyond this conclusion, the present study also shows clear evidence that high-concentration macrocyclization reactions are not only possible but necessary, and suggests the use of catalytic reactions, including solid catalysts and in-flow reactions, to develop macrocyclization reactions under high concentration conditions.

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Dynamic Kinetic Resolution of β-Substituted α-Diketones via Asymmetric Transfer Hydrogenation

Chen

Liu

et al. 2022

J. Am. Chem. Soc.

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Developing innovative dynamic kinetic resolution (DKR) modes and achieving the highly regio-and enantioselective semihydrogenation of unsymmetrical α-diketones are two formidable challenges in the field of contemporary asymmetric (transfer) hydrogenation. In this work, we report the highly regio-and stereoselective asymmetric semi-transfer hydrogenation of unsymmetrical α-diketones through a unique DKR mode, which features the reduction of the carbonyl group distal from the labile stereocenter, while the proximal carbonyl remains untouched. Moreover, the protocol affords a variety of enantioenriched acyclic ketones with α-hydroxy-α′-C(sp 2 )-functional groups, which represent a new product class that has not been furnished in known arts. The utilities of the products have been demonstrated in a series of further transformations including the rapid synthesis of drug molecules. Density functional theory calculations and plenty of control experiments have also been conducted to gain more mechanistic insights into the highly selective semihydrogenation.

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The Acyloin Condensation

Cited by 3 publications

References 259 publications

Thiamine‐Diphosphate‐Dependent Enzymes as Catalytic Tools for the Asymmetric Benzoin‐Type Reaction

Thiamine‐Diphosphate‐Dependent Enzymes as Catalytic Tools for the Asymmetric Benzoin‐Type Reaction

Macrocyclization Reactions at High Concentration (≥0.2M): The Role of Catalysis

Dynamic Kinetic Resolution of β-Substituted α-Diketones via Asymmetric Transfer Hydrogenation

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