Electrochemically Driven Desaturation of Carbonyl Compounds

<p> Electrochemical techniques have long been heralded for their innate sustainability as efficient methods for achieving redox reactions. Carbonyl desaturation, as a fundamental organic oxidation, is an oft-employed transformation to unlock adjacent reactivity. To date, the most reliable methods for achieving it have relied on transition metals (Pd/Cu) or stoichiometric reagents based on I, Br, Se, or S. Herein we report an operationally simple pathway to such structures from enol silanes and phosphates using electrons as the primary reagent. This electrochemically driven desaturation exhibits a broad scope across an array of carbonyl derivatives, is easily scalable (1-100g), and can be predictably implemented into synthetic pathways using experimentally or computationally derived NMR shifts. Mechanistic interrogation suggests a radical-based reaction pathway. <br></p>

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Organo-Redox-Catalysis for the difunctionalization of alkenes and oxidative Ritter reactions by C-H functionalization

Organic Chemistry Frontiers ◽

10.1039/d1qo00259g ◽

2021 ◽

Author(s):

Martin Klussmann ◽

Sensheng Liu

Keyword(s):

Transition Metals ◽

Redox Reactions ◽

Organic Substrates ◽

Redox Catalysis ◽

Redox Catalysts ◽

Oxidative Difunctionalization

Transition metals are the dominant catalysts for redox-reactions between peroxides and organic substrates. Here, we show that triarylamines can act as organic redox-catalysts, enabling oxidative difunctionalization reactions of alkenes and...

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Rational Design of Ti-Based Oxygen Redox Layered Oxides for Advanced Sodium-ion Batteries

Journal of Materials Chemistry A ◽

10.1039/d1ta00669j ◽

2021 ◽

Author(s):

Jaewoon Lee ◽

Sojung Koo ◽

Jinwoo Lee ◽

Duho Kim

Keyword(s):

Transition Metals ◽

Redox Reactions ◽

Rational Design ◽

Alkali Metals ◽

Sodium Ion ◽

Sodium Ion Batteries ◽

Layered Oxides

Considering Mn4+ (3d3)-based cations, various layered oxides (A[AyM1-y]O2, where A and M refer to alkali metals and transition metals, respectively) exhibiting oxygen-redox reactions have been investigated extensively to achieve high...

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Transition Metal-Catalyzed α-Position Carbon–Carbon Bond Formations of Carbonyl Derivatives

Catalysts ◽

10.3390/catal10080861 ◽

2020 ◽

Vol 10 (8) ◽

pp. 861 ◽

Cited By ~ 1

Author(s):

Ha-Eun Lee ◽

Dopil Kim ◽

Ahrom You ◽

Myung Hwan Park ◽

Min Kim ◽

...

Keyword(s):

Transition Metal ◽

Carbonyl Compounds ◽

Bond Formation ◽

Chiral Ligand ◽

Catalytic Systems ◽

Carbon Bond ◽

Carbonyl Derivatives ◽

Carbon Carbon Bond ◽

Transition Metal Catalyzed ◽

Metal Catalyzed

α-Functionalization of carbonyl compounds in organic synthesis has traditionally been accomplished via classical enolate chemistry. As α-functionalized carbonyl moieties are ubiquitous in biologically and pharmaceutically valuable molecules, catalytic α-alkylations have been extensively studied, yielding a plethora of practical and efficient methodologies. Moreover, stereoselective carbon–carbon bond formation at the α-position of achiral carbonyl compounds has been achieved by using various transition metal–chiral ligand complexes. This review describes recent advances—in the last 20 years and especially focusing on the last 10 years—in transition metal-catalyzed α-alkylations of carbonyl compounds, such as aldehydes, ketones, imines, esters, and amides and in efficient carbon–carbon bond formations. Active catalytic species and ligand design are discussed, and mechanistic insights are presented. In addition, recently developed photo-redox catalytic systems for α-alkylations are described as a versatile synthetic tool for the synthesis of chiral carbonyl-bearing molecules.

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Study of Spectral Properties and Redox Reactions of Ferro and Ferri Forms of Modificated by Carbonyl Compounds Hemoglobin under Visible and UV Light Aging

Spectroscopy of Biological Molecules ◽

10.1007/978-94-011-0371-8_110 ◽

1995 ◽

pp. 245-246

Author(s):

A. A. Maskevich ◽

V. I. Stepuro ◽

S. A. Maskevich ◽

A. A. Solodunov ◽

I. I. Stepuro

Keyword(s):

Carbonyl Compounds ◽

Spectral Properties ◽

Redox Reactions ◽

Uv Light

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Transfer Hydrogenation from 2-propanol to Acetophenone Catalyzed by [RuCl2(η6-arene)P] (P = monophosphine) and [Rh(PP)2]X (PP = diphosphine, X = Cl−, BF4−) Complexes

Catalysts ◽

10.3390/catal10020162 ◽

2020 ◽

Vol 10 (2) ◽

pp. 162 ◽

Cited By ~ 1

Author(s):

Alberto Mannu ◽

Arnald Grabulosa ◽

Salvatore Baldino

Keyword(s):

Transition Metals ◽

Carbonyl Compounds ◽

The Other ◽

Transfer Hydrogenation ◽

Chiral Alcohols ◽

High Importance ◽

Bidentate Phosphine ◽

Turn Over Frequency ◽

Turn Over ◽

Reduction Of Ketones

The reduction of ketones through homogeneous transfer hydrogenation catalyzed by transition metals is one of the most important routes for obtaining alcohols from carbonyl compounds. The interest of this method increases when opportune catalytic precursors are able to perform the transformation in an asymmetric fashion, generating enantiomerically enriched chiral alcohols. This reaction has been extensively studied in terms of catalysts and variety of substrates. A large amount of information about the possible mechanisms is available nowadays, which has been of high importance for the development of systems with excellent outcomes in terms of conversion, enantioselectivity and Turn Over Frequency. On the other side, many mechanistic aspects are still unclear, especially for those catalytic precursors which have shown only moderate performances in transfer hydeogenation. This is the case of neutral [RuCl2(η6-arene)(P)] and cationic [Rh(PP)2]X (X = anion; P and PP = mono- and bidentate phosphine, respectively) complexes. Herein, a summary of the known information about the Transfer Hydrogenation catalyzed by these complexes is provided with a continuous focus on the more relevant mechanistic features.

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Cyclopropenium-Activated DMSO for Swern-Type Oxidation

Synlett ◽

10.1055/s-0037-1611183 ◽

2019 ◽

Vol 30 (03) ◽

pp. 329-332 ◽

Cited By ~ 1

Author(s):

Tianfo Guo ◽

Yu Gao ◽

Zhenjiang Li ◽

Jingjing Liu ◽

Kai Guo

Keyword(s):

Conventional Method ◽

Carbonyl Compounds ◽

Oxalyl Chloride ◽

Fast Reactions ◽

Broad Scope ◽

New Type ◽

High Yields ◽

Swern Oxidation ◽

Easy Operation

Swern oxidation is widely used to convert alcohols into their corresponding carbonyl compounds. However, the conventional method with use of the volatile oxalyl chloride as an activator requires the reaction to be conducted below −60 °C. We discovered that 3,3-dichloro-1,2-diphenylcyclopropene (DDC) can be used as a new activator for Swern-type oxidations of alcohols, which can be conducted at −20 °C. This new protocol features mild and fast reactions with easy operation. Furthermore, the activator DDC is easy to handle, and diphenylcyclopropenone can be recovered quantitively. This new type of Swern oxidation shows a broad scope of substrates including benzylic, allylic, aliphatic, and biobased alcohols, and gives high yields of up to 93%.

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Novel and selective α-substitution of ketones and other carbonyl compounds based on Pd-catalyzed cross coupling of α,β-unsaturated carbonyl derivatives containing α-halogen or α-metal groups

Journal of Organometallic Chemistry ◽

10.1016/s0022-328x(98)01057-2 ◽

1999 ◽

Vol 576 (1-2) ◽

pp. 179-194 ◽

Cited By ~ 39

Author(s):

Ei-ichi Negishi

Keyword(s):

Carbonyl Compounds ◽

Cross Coupling ◽

Carbonyl Derivatives

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Reaction Pathway of Methylenation of Carbonyl Compounds with Bis(iodozincio)methane

Journal of the American Chemical Society ◽

10.1021/ja104439w ◽

2010 ◽

Vol 132 (49) ◽

pp. 17452-17458 ◽

Cited By ~ 23

Author(s):

Mutsumi Sada ◽

Shinsuke Komagawa ◽

Masanobu Uchiyama ◽

Masami Kobata ◽

Tsuyoshi Mizuno ◽

...

Keyword(s):

Carbonyl Compounds ◽

Reaction Pathway

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Electrochemical Measurement of Corrosion

CORROSION ◽

10.5006/0010-9312-26.5.171 ◽

1970 ◽

Vol 26 (5) ◽

pp. 171-176 ◽

Cited By ~ 10

Author(s):

M. E. INDIG ◽

C. GROOT

Keyword(s):

Weight Gain ◽

Corrosion Rate ◽

Redox Reactions ◽

Electrochemical Techniques ◽

Electrochemical Measurement ◽

Alloy 600 ◽

Measured Weight ◽

Dissolved Hydrogen ◽

The Difference ◽

Good Agreement

Abstract The results of electrochemical measurements on the corrosion of NiCrFe Alloy 600 and Zircaloy-2 in slightly alkaline lithiated water at 288 C (550 F) are presented. The study showed that, in the presence of dissolved hydrogen at the level of 35 Scc/kg-H2O, the electrochemical techniques could not be used to measure the corrosion rate of NiCrFe Alloy 600. However, the measurements on Zircaloy-2 were unaffected by the presence of hydrogen, and good agreement between the electrochemically determined weight gain and the directly measured weight gain resulted. The difference between the behavior of the two alloys is explained by the ease with which redox reactions involving hydrogen occur on the NiCrFe Alloy 600 surfaces.

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