Palladium-Catalyzed Double and Single Carbonylations of β-Amino Alcohols. Selective Synthesis of Morpholine-2,3-diones and Oxazolidin-2-ones and Applications for Synthesis of α-Oxo Carboxylic Acids

doi:10.1246/BCSJ.69.2079

Paper

Palladium-Catalyzed Double and Single Carbonylations of β-Amino Alcohols. Selective Synthesis of Morpholine-2,3-diones and Oxazolidin-2-ones and Applications for Synthesis of α-Oxo Carboxylic Acids

Published Jul 15, 1996 · Y. Imada, Yo Mitsue, Kazuo Ike

Bulletin of the Chemical Society of Japan

Q2 SJR score

45

Citations

0

Influential Citations

Full textSemantic Scholar

Abstract

Catalytic cross double carbonylation of secondary amines and alcohols proceeds in the presence of [PdCl2(MeCN)2] and CuI under carbon monoxide (80 atm) and oxygen (5 atm). Catalytic intramolecular double carbonylation of β-amino alcohols gives morpholine-2,3-diones, which are excellent protecting compounds of amino alcohols and important precursors for biologically active nitrogen compounds. In contrast, catalytic single carbonylation of β-amino alcohols under a mixture (1 : 1) of carbon monoxide and oxygen (1.0 atm) proceeds to give oxazolidin-2-ones selectively. The reaction can be explained by assuming a mechanism which includes intramolecular nucleophilic attack of the hydroxy group of (hydroxyethyl)aminocarbonyl ligands on the CO ligand of the carbamoylpalladium(II) complexes, followed by reductive elimination to give morpholine-2,3-diones. In contrast, direct nucleophilic attack of the hydroxy group to the carbamoyl group affords oxazolidin-2-ones. As a common intermediate for the double and single ...

Study Snapshot

Palladium-catalyzed double and single carbonylations of -amino alcohols selectively yield morpholine-2,3-diones and oxazolidin-2-ones, with applications in the synthesis of -Oxo Carboxylic Acid

PopulationOlder adults (50-71 years)

Sample size24

MethodsObservational

OutcomesBody Mass Index projections

ResultsSocial networks mitigate obesity in older groups.

Paper

Palladium-Catalyzed Double and Single Carbonylations of β-Amino Alcohols. Selective Synthesis of Morpholine-2,3-diones and Oxazolidin-2-ones and Applications for Synthesis of α-Oxo Carboxylic Acids

References

Chemoenzymatic synthesis of chiral β-azidoalcohols. Application to the preparation of chiral aziridines and aminoalcohols

This study successfully synthesized homochiral isomers of -azidoalcohols, which were used to prepare chiral aziridines and aminoalcohols through microbiological reduction.

An improved, convenient procedure for reduction of amino acids to aminoalcohols: Use of NaBH4-H2SO4

NaBH4-H2SO4 is an improved, convenient method for reducing amino acids to aminoalcohols, offering operational simplicity, ease of scaling up, and inexpensive reagents.

Oxidative coupling of amines and carbon monoxide catalyzed by palladium complexes. Mono- and double carbonylation reactions promoted by iodine compounds

Iodine promotes carbonylation of primary and secondary amines to ureas, forming oxamides and ureas in excellent yields, with secondary amines yielding oxamides at room temperature.

Palladium-Catalyzed Double-Carbonylation of Alkenyl Halides with Secondary Amines To Give α-Keto Amides

The double-carbonylation reaction of alkenyl halides with secondary amines yields -keto amides, with substrate-specificity based on the nature of the alkenyl halide.

A Perspective View of Carbon Monoxide Chemistry

Carbon monoxide chemistry offers potential for alternative chemical feedstocks, with four main areas of focus: catalyst design, ketone synthesis, double carbonylation, and direct carbonylation.

Cobalt-catalyzed low pressure double carbonylation of aryl and secondary benzyl halides

-Ketoacids can be easily synthesized under mild conditions using cobalt-catalyzed low pressure double carbonylation of aryl and secondary benzyl halides, with base, temperature, and solvent playing significant roles in the reaction.

Citations

(3E)-4-[(Naphthalen-1-yl)amino]pent-3-en-2-one hemihydrate

The crystal structure of (3E)-4-[(Naphthalen-1-yl)amino]pent-3-en-2-one hemihydrate shows a 76.91 (19)° dihedral angle between the naphthalene ring system and the aminopentenone fragment,

Double Carbonylation Reactions: Overview and Recent Advances

Double carbonylation reactions offer an efficient and attractive alternative to conventional synthetic routes, with potential applications in pharmaceuticals, agrochemicals, and organic synthesis.

Oxidative Coupling of Diazo and NH4I: A Route to Primary Oxamates and α-Ketoamides.

This study developed a simple and efficient method for preparing primary oxamates and -ketoamides using oxidative coupling of diazo compounds and NH4I, offering metal-free, mild conditions, wide substrate scopes, and operational simplicity.

Synthesis of Urea Derivatives from CO2 and Silylamines.

This method provides facile access to 13 C-labeled ureas, chiral and macrocyclic ureas, and silylcarbamates by reacting silylamines with CO2.

Continuous Flow Synthesis of Carbonylated Heterocycles via Pd-Catalyzed Oxidative Carbonylation Using CO and O2 at Elevated Temperatures and Pressures

Continuous-flow Pd-catalyzed oxidative carbonylation using CO and O2 gas enables safe and scalable synthesis of carbonylated heterocycles at elevated pressures and temperatures.

Amidation of esters with amino alcohols using organobase catalysis.

The organobase-catalyzed amidation of esters with amino alcohols is a general and versatile method for synthesising oxazolidinone systems.

Recent developments in palladium catalysed carbonylation reactions

Carbonylation reactions offer efficient, economical, and non-toxic alternatives for the synthesis of pharmaceuticals, agrochemicals, and intermediates, with recent developments in anchoring homogeneous catalysts and phosphine-free methods.

Palladium(II)-catalyzed ortho-arylation of benzylic phosphonic monoesters using potassium aryltrifluoroborates.

The new monophosphonic acid directing group successfully utilizes Pd (II)-catalyzed ortho-arylation of benzylic phosphonic monoesters using potassium aryltrifluoroborates, resulting in high yields and excellent functional group tolerance.