Nucleophilic reactions of carboxylic esters, trialkyl phosphates, and some organomercury compounds with onium salts

1969 ◽  
Vol 18 (9) ◽  
pp. 1818-1820 ◽  
Author(s):  
A. N. Nesmeyanov ◽  
L. G. Makarova ◽  
V. N. Vinogradova
Keyword(s):  
Nucleophilic Reactions ◽  
Onium Salts ◽  
Trialkyl Phosphates ◽  
Organomercury Compounds ◽  
Carboxylic Esters

Action des métaux sur les esters carboxyliques en présence d'hexaméthylphosphortriamide: une méthode simple et efficace de réduction des alcools en alcanes

1984 ◽  
Vol 62 (10) ◽  
pp. 2063-2072 ◽  
Author(s):  
Henri Deshayes ◽  
Jean-Pierre Pete
Keyword(s):  
Carboxylic Acid ◽  
Carboxylic Acids ◽  
Steric Hindrance ◽  
Radical Anion ◽  
Carboxylic Group ◽  
Hexamethylphosphoric Triamide ◽  
Nucleophilic Reactions ◽  
Tert Butanol ◽  
Carboxylic Esters

Carboxylic acids, alcohols (R′OH), and alkanes (R′H) are the main products of the reduction of carboxylic esters (RCO2R′) by sodium in hexamethylphosphoric triamide (HMPA). Alkanes are preferentially formed from the carboxylic esters of hindered alcohols. The alkane content, however, is lowered when there is less steric hindrance on the carboxylic group, and increased when tert-butanol is introduced into the reaction mixture. The reduction of esters in HMPA has been compared to the reduction in alkylamines. The alkane is produced mainly by the decomposition of a radical anion intermediate which can be solvated by HMPA. The alcohol is the result of several possible bimolecular nucleophilic reactions; however, unimolecular and bimolecular processes are involved in the production of the carboxylic acid.

DIAMAGNETIC SUSCEPTIBILITIES OF SOME COMPOUNDS CONTAINING OXYGEN LINKED TO NITROGEN OR PHOSPHORUS

1964 ◽  
Vol 42 (8) ◽  
pp. 1817-1821 ◽  
Author(s):  
M. W. Lister ◽  
R. Marson
Keyword(s):  
Amine Oxide ◽  
Phosphine Oxides ◽  
Trialkyl Phosphates ◽  
Trialkyl Phosphites ◽  
Dialkyl Phosphites ◽  
Carboxylic Esters ◽  
Usual Formula ◽  
Extra Oxygen ◽  
Oxygen Atoms

The diamagnetic susceptibilities of a number of compounds containing oxygen linked to nitrogen or phosphorus have been measured. The results are interpreted in terms of the apparent contribution of the oxygen atoms to the susceptibility in these and other series of compounds, and are compared with other evidence on the nature of the bonds to oxygen. The results support the usual formula of an amine oxide as R3N → O, but phosphine oxides behave as would be expected for R3P = O. Phosphorus oxyhalides have molar susceptibilities about 4.6 (in units of −10−6 e.m.u.) larger than the corresponding trihalides, a difference close to that for singly bound oxygen in ethers or alcohols. Each oxygen contributes 4.4 in trialkyl phosphites, as might be expected for P(OR)3; but the value in dialkyl phosphites is 4.9 per oxygen, thereby showing behavior similar to that of carboxylic esters. The extra oxygen in trialkyl phosphates as compared with trialkyl phosphites contributes 9.4, a surprisingly large amount.

Recent Developments in the Asymmetric Detrifluoroacetylative Reactions of in situ Generated Mono-Fluorinated Enolates

2020 ◽  
Vol 24 (18) ◽  
pp. 2181-2191
Author(s):  
Li Wang ◽  
Ziyi Li ◽  
Jiang Liu ◽  
Jianlin Han ◽  
Hiroki Moriwaki ◽  
...  
Keyword(s):  
Organic Chemistry ◽  
Bond Cleavage ◽  
Synthetic Methodology ◽  
Research Topics ◽  
Synthetic Organic Chemistry ◽  
Nucleophilic Reactions ◽  
F Center ◽  
Recent Developments

The development of an efficient and mild synthetic methodology for the construction of bioactive fluorine-containing molecules represents one of the hot research topics in general synthetic organic chemistry. In this review, some recent progresses achieved in the development of detrifluoroacetylatively generated mono-fluorinated enolates via CC bond cleavage and their asymmetric nucleophilic reactions for assembly of chiral quaternary C-F center containing compounds.

Green Application of Phase-Transfer Catalysis in Oxidation: A Comprehensive Review

2020 ◽  
Vol 17 (4) ◽  
pp. 405-411
Author(s):  
Chuan-Hui Wang ◽  
Chen-Fu Liu ◽  
Guo-Wu Rao
Keyword(s):  
Organic Chemistry ◽  
Green Chemistry ◽  
Oxidation Reaction ◽  
Phase Transfer Catalysis ◽  
Phase Transfer ◽  
Important Application ◽  
Oxidation Reactions ◽  
Comprehensive Review ◽  
Phase Transfer Catalysts ◽  
Onium Salts

Oxidation reactions have emerged as one of the most versatile tools in organic chemistry. Various onium salts such as ammonium, phosphonium, arsonium, bismuthonium, tellurium have been used as phase transfer catalysts in many oxidation reactions. Certainly, considerable catalysts have been widely used in Phase-Transfer Catalysis (PTC). This review focuses on the application of PTC in various oxidation reaction. Furthermore, PTC also conforms to the concept of “Green Chemistry”. <p></p> • Oxidation has become one of the most widely used tools in organic chemistry and phase transfer catalysts has been widely used in oxidation. <p></p> • The application of phase transfer catalysts in oxidation reaction will be summarized. <p></p> • Phase transfer catalysts have important application in various oxidation reaction.

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