scholarly journals A biphasic oxidation of alcohols to aldehydes and ketones using a simplified packed-bed microreactor

2009 ◽  
Vol 5 ◽  
Author(s):  
Andrew Bogdan ◽  
D Tyler McQuade
Keyword(s):  
Packed Bed ◽  
Secondary Alcohols ◽  
Great Stability ◽  
Wide Range ◽  
Oxidation Of Alcohols ◽  
Aldehydes And Ketones ◽  
High Yields ◽  
By Products ◽  
Over Time

We demonstrate the preparation and characterization of a simplified packed-bed microreactor using an immobilized TEMPO catalyst shown to oxidize primary and secondary alcohols via the biphasic Anelli-Montanari protocol. Oxidations occurred in high yields with great stability over time. We observed that plugs of aqueous oxidant and organic alcohol entered the reactor as plugs but merged into an emulsion on the packed-bed. The emulsion coalesced into larger plugs upon exiting the reactor, leaving the organic product separate from the aqueous by-products. Furthermore, the microreactor oxidized a wide range of alcohols and remained active in excess of 100 trials without showing any loss of catalytic activity.

scholarly journals Copper(I)-Catalyzed Click Chemistry as a Tool for the Functionalization of Nanomaterials and the Preparation of Electrochemical (Bio)Sensors

Sensors ◽  
2019 ◽  
Vol 19 (10) ◽  
pp. 2379 ◽  
Author(s):  
P. Yáñez-Sedeño ◽  
A. González-Cortés ◽  
S. Campuzano ◽  
J. M. Pingarrón
Keyword(s):  
Electrochemical Sensors ◽  
Functional Integration ◽  
Future Directions ◽  
Physiological Conditions ◽  
Electrode Surfaces ◽  
Wide Range ◽  
High Yields ◽  
By Products ◽  
Powerful Strategy

Proper functionalization of electrode surfaces and/or nanomaterials plays a crucial role in the preparation of electrochemical (bio)sensors and their resulting performance. In this context, copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) has been demonstrated to be a powerful strategy due to the high yields achieved, absence of by-products and moderate conditions required both in aqueous medium and under physiological conditions. This particular chemistry offers great potential to functionalize a wide variety of electrode surfaces, nanomaterials, metallophthalocyanines (MPcs) and polymers, thus providing electrochemical platforms with improved electrocatalytic ability and allowing the stable, reproducible and functional integration of a wide range of nanomaterials and/or different biomolecules (enzymes, antibodies, nucleic acids and peptides). Considering the rapid progress in the field, and the potential of this technology, this review paper outlines the unique features imparted by this particular reaction in the development of electrochemical sensors through the discussion of representative examples of the methods mainly reported over the last five years. Special attention has been paid to electrochemical (bio)sensors prepared using nanomaterials and applied to the determination of relevant analytes at different molecular levels. Current challenges and future directions in this field are also briefly pointed out.

scholarly journals Applications of tert-butanesulfinamide in the asymmetric synthesis of amines

2003 ◽  
Vol 75 (1) ◽  
pp. 39-46 ◽  
Author(s):  
J. A. Ellman
Keyword(s):  
Amino Acids ◽  
Asymmetric Synthesis ◽  
Nucleophilic Addition ◽  
Amino Alcohols ◽  
Wide Range ◽  
Aldehydes And Ketones ◽  
Directing Group ◽  
High Yields ◽  
Direct Condensation

tert-Butanesulfinamide is prepared using catalytic enantioselective methods in two steps from the extremely inexpensive oil waste by-product, tert-butyl disulfide. Direct condensation of tert-butanesulfinamide with aldehydes and ketones provides tert-butanesulfinyl imines in uniformly high yields. The tert-butanesulfinyl group activates the imines for the addition of many different classes of nucleophiles, serves as a powerful chiral directing group, and after nucleophilic addition is readily cleaved by treatment with acid. A wide range of highly enantioenriched amines, including α-branched and α,α-dibranched amines, α- and β-amino acids, 1,2 and 1,3-amino alcohols and α-trifluoromethyl amines are efficiently synthesized using this methodology.

scholarly journals Photochemical oxidation of benzylic primary and secondary alcohols utilizing air as the oxidant

2020 ◽  
Vol 22 (2) ◽  
pp. 471-477 ◽  
Author(s):  
Nikolaos F. Nikitas ◽  
Dimitrios Ioannis Tzaras ◽  
Ierasia Triandafillidi ◽  
Christoforos G. Kokotos
Keyword(s):  
Photochemical Oxidation ◽  
Secondary Alcohols ◽  
Oxidation Of Alcohols ◽  
Aldehydes And Ketones

A mild and green photochemical protocol for the oxidation of alcohols to aldehydes and ketones was developed.

scholarly journals A Photo-Enzymatic Cascade to Transform Racemic Alcohols into Enantiomerically Pure Amines

Catalysts ◽  
2019 ◽  
Vol 9 (4) ◽  
pp. 305 ◽  
Author(s):  
Jenő Gacs ◽  
Wuyuan Zhang ◽  
Tanja Knaus ◽  
Francesco G. Mutti ◽  
Isabel W.C.E. Arends ◽  
...  
Keyword(s):  
Aromatic Compounds ◽  
Reductive Amination ◽  
Aerobic Oxidation ◽  
Secondary Alcohols ◽  
One Pot ◽  
Enantiomerically Pure ◽  
Step Procedure ◽  
Wide Range ◽  
Aldehydes And Ketones ◽  
One Step

The consecutive photooxidation and reductive amination of various alcohols in a cascade reaction were realized by the combination of a photocatalyst and several enzymes. Whereas the photocatalyst (sodium anthraquinone-2-sulfonate) mediated the light-driven, aerobic oxidation of primary and secondary alcohols, the enzymes (various ω-transaminases) catalyzed the enantio-specific reductive amination of the intermediate aldehydes and ketones. The system worked in a one-pot one-step fashion, whereas the productivity was significantly improved by switching to a one-pot two-step procedure. A wide range of aliphatic and aromatic compounds was transformed into the enantiomerically pure corresponding amines via the photo-enzymatic cascade.

o-Nitrophenylethylene glycol as photoremovable protective group for aldehydes and ketones: syntheses, scope, and limitations

1983 ◽  
Vol 61 (2) ◽  
pp. 400-410 ◽  
Author(s):  
D. Gravel ◽  
J. Hebert ◽  
D. Thoraval
Keyword(s):  
Point Of View ◽  
High Yield ◽  
Protective Group ◽  
Isolation And Characterization ◽  
Usual Manner ◽  
Aldehydes And Ketones ◽  
Inert Solvent ◽  
Acidic Conditions ◽  
High Yields

The preparation of o-nitrophenylethylene glycol is described along with its application as a photolabile protective group for aldehydes and ketones. Formation of the acetals and ketals is achieved in good to high yields in the usual manner and deprotection is carried out in fair to high yield, by photolysis at 350 nm in an inert solvent such as benzene. Because of the particular nature of the present protective group, its stability to basic and acidic conditions has been examined and is reported to complete the scope and limitations aspect. From a mechanistic point of view, the isolation and characterization of o-nitroso-α-hydroxyacetophenone as the spent reagent demonstrates a mechanistic link with the known o-nitrobenzaldehyde to o-nitrosobenzoic acid photorearrangement.

scholarly journals A New Thermophilic Ene-Reductase from the Filamentous Anoxygenic Phototrophic Bacterium Chloroflexus aggregans

2021 ◽  
Vol 9 (5) ◽  
pp. 953
Author(s):  
Marina Simona Robescu ◽  
Mattia Niero ◽  
Giovanni Loprete ◽  
Laura Cendron ◽  
Elisabetta Bergantino
Keyword(s):  
Crystal Structure ◽  
Crystal Packing ◽  
Solvent Tolerance ◽  
Class Iii ◽  
Ph Optimum ◽  
Anoxygenic Phototrophic Bacterium ◽  
Wide Range ◽  
The Family ◽  
High Yields

Aiming at expanding the biocatalytic toolbox of ene-reductase enzymes, we decided to explore photosynthetic extremophile microorganisms as unique reservoir of (new) biocatalytic activities. We selected a new thermophilic ene-reductase homologue in Chloroflexus aggregans, a peculiar filamentous bacterium. We report here on the functional and structural characterization of this new enzyme, which we called CaOYE. Produced in high yields in recombinant form, it proved to be a robust biocatalyst showing high thermostability, good solvent tolerance and a wide range of pH optimum. In a preliminary screening, CaOYE displayed a restricted substrate spectrum (with generally lower activities compared to other ene-reductases); however, given the amazing metabolic ductility and versatility of Chloroflexus aggregans, further investigations could pinpoint peculiar chemical activities. X-ray crystal structure has been determined, revealing conserved features of Class III (or thermophilic-like group) of the family of Old Yellow Enzymes: in the crystal packing, the enzyme was found to assemble as dimer even if it behaves as a monomer in solution. The description of CaOYE catalytic properties and crystal structure provides new details useful for enlarging knowledge, development and application of this class of enzymes.

scholarly journals Mechanically induced oxidation of alcohols to aldehydes and ketones in ambient air: Revisiting TEMPO-assisted oxidations

2017 ◽  
Vol 13 ◽  
pp. 2049-2055 ◽  
Author(s):  
Andrea Porcheddu ◽  
Evelina Colacino ◽  
Giancarlo Cravotto ◽  
Francesco Delogu ◽  
Lidia De Luca
Keyword(s):  
Ball Milling ◽  
Carboxylic Acids ◽  
Carbonyl Compounds ◽  
Ambient Air ◽  
Mechanochemical Reaction ◽  
Secondary Alcohols ◽  
Mechanical Processing ◽  
Oxidation Of Alcohols ◽  
Aldehydes And Ketones ◽  
Cost Efficient

The present work addresses the development of an eco-friendly and cost-efficient protocol for the oxidation of primary and secondary alcohols to the corresponding aldehydes and ketones by mechanical processing under air. Ball milling was shown to promote the quantitative conversion of a broad set of alcohols into carbonyl compounds with no trace of an over-oxidation to carboxylic acids. The mechanochemical reaction exhibited higher yields and rates than the classical, homogeneous, TEMPO-based oxidation.

scholarly journals An aerobic oxidation of alcohols into carbonyl synthons using bipyridyl-cinchona based palladium catalyst

RSC Advances ◽  
2021 ◽  
Vol 11 (52) ◽  
pp. 32942-32954
Author(s):  
Ravi Kumar Cheedarala ◽  
Ramasamy R. Chidambaram ◽  
Ayyanar Siva ◽  
Jung Il Song
Keyword(s):  
Catalytic System ◽  
Palladium Catalyst ◽  
Aerobic Oxidation ◽  
Cinchona Alkaloid ◽  
Secondary Alcohols ◽  
Moderate Pressure ◽  
Oxidation Of Alcohols ◽  
Aldehydes And Ketones

We have reported an aerobic oxidation of primary and secondary alcohols to respective aldehydes and ketones using a bipyridyl-cinchona alkaloid based palladium catalytic system (PdAc-5) using oxygen at moderate pressure.

Stereospecific, Palladium-catalyzed C(sp3)–H Alkenylation and Alkynylation of a Proline Derivative Enabled by 8-Aminoquinoline as a Directing Group

2020 ◽  
Author(s):  
Aleksandra Balliu ◽  
Aaltje Roelofje Femmigje Strijker ◽  
Michael Oschmann ◽  
Monireh Pourghasemi Lati ◽  
Oscar Verho
Keyword(s):  
Carboxylic Acid ◽  
Building Blocks ◽  
Wide Range ◽  
Palladium Catalyzed ◽  
Directing Group ◽  
High Yields ◽  
Vinyl Iodides ◽  
Initial Results

<p>In this preprint, we present our initial results concerning a stereospecific Pd-catalyzed protocol for the C3 alkenylation and alkynylation of a proline derivative carrying the well utilized 8‑aminoquinoline directing group. Efficient C–H alkenylation was achieved with a wide range of vinyl iodides bearing different aliphatic, aromatic and heteroaromatic substituents, to furnish the corresponding C3 alkenylated products in good to high yields. In addition, we were able show that this protocol can also be used to install an alkynyl group into the pyrrolidine scaffold, when a TIPS-protected alkynyl bromide was used as the reaction partner. Furthermore, two different methods for the removal of the 8-aminoquinoline auxiliary are reported, which can enable access to both <i>cis</i>- and <i>trans</i>-configured carboxylic acid building blocks from the C–H alkenylation products.</p>

Synthetic and Mechanistic Studies of a Versatile Heteroaryl Thioether Directing Group for Pd(II) Catalysis

2019 ◽  
Author(s):  
Andrew Romine ◽  
Kin Yang ◽  
Malkanthi Karunananda ◽  
Jason Chen ◽  
Keary Engle
Keyword(s):  
Mechanistic Studies ◽  
Salvianolic Acid ◽  
Wide Range ◽  
Computational Data ◽  
Synthetic Utility ◽  
Directing Group ◽  
High Yields ◽  
Julia Olefination ◽  
Reaction Progress Kinetic Analysis

A weakly coordinating monodentate heteroaryl thioether directing group has been developed for use in Pd(II) catalysis to orchestrate key elementary steps in the catalytic cycle that require conformational flexibility in a manner that is difficult to accomplish with traditional strongly coordinating directing groups. This benzothiazole thioether, (BT)S, directing group can be used to promote oxidative Heck reactivity of internal alkenes providing a wide range of products in moderate to high yields. To demonstrate the broad applicability of this directing group, arene C–H olefination was also successfully developed. Reaction progress kinetic analysis provides insights into the role of the directing group in each reaction, which is supplemented with computational data for the oxidative Heck reaction. Furthermore, this (BT)S directing group can be transformed into a number of synthetically useful functional groups, including a sulfone for Julia olefination, allowing it to serve as a “masked olefin” directing group in synthetic planning. In order to demonstrate this synthetic utility, natural products (+)-salvianolic acid A and salvianolic acid F are formally synthesized using the (BT)S directed C–H olefination as the key step.

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