3.2.3. Hydroformylation 2467 3.2.4. Dimerization 2468 3.2.5. Oxidative Cleavage and Ozonolysis 2469 3.2.6. Metathesis 2470 4. Terpenes 2472 4.1. Pinene 2472 4.1.1. Isomerization: R-Pinene 2472 4.1.2. Epoxidation of R-Pinene 2475 4.1.3. Isomerization of R-Pinene Oxide 2477 4.1.4. Hydration of R-Pinene: R-Terpineol 2478 4.1.5. Dehydroisomerization 2479 4.2. Limonene 2480 4.2.1. Isomerization 2480 4.2.2. Epoxidation: Limonene Oxide 2480 4.2.3. Isomerization of Limonene Oxide 2481 4.2.4. Dehydroisomerization of Limonene and Terpenes To Produce Cymene 2481

Chemical Routes for the Transformation of Biomass into Chemicals

The reagent formed by combining diethyl azodicarboxylate (DEAD) and triphenylphosphine (TPP) could be utilized in the intermolecular dehydration between an alcohol and various acidic components such as carboxylic acids, phosphoric diesters, imides, and active methylene compounds. By the use of DEAD and TPP, diols and hydroxy acids gave cyclic ethers and lactones, respectively. The reaction of nucleosides with DEAD and TPP afforded triphenylphosphoranylnucleosides. Alcohols reacted with 2,6-di-t-butyl-4-nitrophenol in the presence of DEAD and TPP to give aci-nitroesters which converted into the corresponding carbonyl compounds.

The Use of Diethyl Azodicarboxylate and Triphenylphosphine in Synthesis and Transformation of Natural Products

The increase in atmospheric carbon dioxide is linked to climate changes; hence there is an urgent need to reduce the accumulation of CO2 in the atmosphere. The utilization of CO2 as a raw material in the synthesis of chemicals and liquid energy carriers offers a way to mitigate the increasing CO2 buildup. This review covers six important CO2 transformations namely: chemical transformations, photochemical reductions, chemical and electrochemical reductions, biological conversions, reforming and inorganic transformations. Furthermore, the vast research area of carbon capture and storage is reviewed briefly. This review is intended as an introduction to CO2, its synthetic reactions and their possible role in future CO2 mitigation schemes that has to match the scale of man-made CO2 in the atmosphere, which rapidly approaches 1 teraton.

The teraton challenge. A review of fixation and transformation of carbon dioxide

The Medicinal Chemist’s Toolbox: An Analysis of Reactions Used in the Pursuit of Drug Candidates

The Medicinal Chemist's Toolbox: An Analysis of Reactions Used in the Pursuit of Drug Candidates

1,2-Amino Alcohols and Their Heterocyclic Derivatives as Chiral Auxiliaries in Asymmetric Synthesis

When n-valeric acid was treated with allyl diethyl phosphite and diethyl azodicarboxylate, allyl valeriate and diethyl N-(diethyl)phosphoryl hydrazodicarboxylate were obtained in good yields. Similarly ethyl benzoate was obtained in a nearly quantitative yield by the reaction of benzoic acid with triethyl phosphite and diethyl azodicarboxylate. The reaction of carboxylic acid with triphenyl phosphine and diethyl azodicarboxylate in the presence of an alcohol resulted in the formation of the corresponding esters of the carboxylic acid, triphenyl phosphine oxide, and diethyl hydrazodicarboxylate. The mechanisms of these reactions are also discussed.

Preparation of Esters of Carboxylic and Phosphoric Acid via Quaternary Phosphonium Salts

Stereospecific and stereoselective reactions. I. Preparation of amines from alcohols

Trivalent phosphorus compounds, phosphine or trialkylphosphites, have been oxidized by means of diethyl azodicarboxylate and either benzyl or allyl alcohol to give the corresponding phosphine oxide or trialkyl phosphates. The reaction was then extended to the phosphorylation of alcohols. When allyl diethyl phosphite was treated with diethyl azodicarboxylate in the presence of an alcohol at room temperature, a corresponding alkyl diethyl phosphate and diethyl N-allyl hydrazodicarboxylate were obtained in good yields. On the other hand, when phenol was treated with allyl diethyl phosphite and diethyl azodicarboxylate, diethyl phenyl phosphate, allyl phenyl ether and diethyl hydrazodicarboxylate were obtained. The mechanism of their formation will also be discussed.

Preparation of Esters of Phosphoric Acid by the Reaction of Trivalent Phosphorus Compounds with Diethyl Azodicarboxylate in the Presence of Alcohols

The reaction of dibenzyl hydrogen phosphate with alcohols in the presence of diethyl azodicarboxylate and triphenylphosphine, followed by catalytic hydrogenation, resulted in the formation of the corresponding alkyl dihydrogen phosphates. When p-tolyl dihydrogen phosphate and ethanol were allowed to react with diethyl azodicarboxylate and triphenylphosphine, ethyl p-tolyl hydrogen phosphate and diethyl p-tolyl phosphate were obtained. On the other hand, dipyridinium p-tolyl phosphate gave ethyl p-tolyl hydrogen phosphate and di p-tolyl pyrophosphate. The reaction of alkyl N,N′-tetraethylphosphorodiamidites with carboxylic acids in the presence of diethyl azodicarboxylate resulted in the formation of corresponding carboxylic esters. When these reactions (benzoylation) were carried out with the use of optically active 2-octanol, 2-octyl benzoate was obtained with inverted configuration.

Oyo Mitsunobu

Papers

The Use of Diethyl Azodicarboxylate and Triphenylphosphine in Synthesis and Transformation of Natural Products

Preparation of Esters of Carboxylic and Phosphoric Acid via Quaternary Phosphonium Salts

Stereospecific and stereoselective reactions. I. Preparation of amines from alcohols

Preparation of Esters of Phosphoric Acid by the Reaction of Trivalent Phosphorus Compounds with Diethyl Azodicarboxylate in the Presence of Alcohols

Preparation of Carboxylic Esters and Phosphoric Esters by the Activation of Alcohols