Oxidative Decarboxylation of Acids by Lead Tetraacetate

Abstract

Lead tetracetate, one of the most versatile oxidizing agents know in organic chemistry, is capable of reacting with a variety of common functional groups; its use in organic chemistry has been reviewed. The purpose of this chapter is to review the oxidative process involving the decarboxylation of acids, whereby carboxylic acids are converted to a variety of compounds depending on experimental conditions, e.g, solvent, structure of substrates, and presence of additives. The primary objective here is to evaluate critically the usefulness of this reaction in organic synthesis. Decarboxylation of alpha‐hydroxy and alpha‐amino acids by lead tetraacetate has been known for many years. Khararaschn and co‐workers reported exhaustive products studies of the decomposition of lead tetraacetate in acetic acid. Sodium acetate accelerates the reduction of lead tetraacetate but no carbon dioxides liberated. Mosher and Kahr also examined the thermal decomposition of various organic acids by lead tetraacetate. Since then many studies on the mechanism and synthetic utility of these reaction and its modifications have been reported.

Total Synthesis of Alvaradoins E and F, Uveoside, and 10-epi-Uveoside

“…With carboxylic acid 13 in hand, we then explored various reaction conditions for transforming compound 13 into the corresponding glycosyl halide via the Hunsdiecker reaction. 24,25 It was then discovered that utilizing Kochi's method, 29 which involves treatment of carboxylic acid 13 with lead tetraacetate in acetic acid and THF, leads to a clean and stereoselective conversion to α-acetate ester 14. An explanation for the stereoselective conversion could be due to the neighboring C-2' axial benzyl group hindering attack of the nucleophile from the same face (Scheme 3.7.2).…”

Taking electrodecarboxylative etherification beyond Hofer–Moest using a radical C–O coupling strategy

“…Decarboxylative C–O bond formation is a particularly attractive synthetic strategy since carboxylic acids are widely available in great structural diversity 4 . Thermal and photochemical strategies for decarboxylative C–O bond formation, including metal-mediated oxidative decarboxylations using Mn III 5 , 6 , In III 7 , Tl III 8 , Pb IV 9 , 10 or Ce IV 11 , 12 , as well as precious metal-catalysed procedures such as Ru 13 , 14 , Ir 15 , 16 , Ag 17 , 18 or Au 19 , are relatively well developed. Photochemical reaction variants proceed under mild conditions but require expensive photocatalysts or pre-functionalised substrates (i.e.…”

Oxidative Decarboxylation of 2-Aryl Carboxylic Acids Using (Diacetoxyiodo)benzene for Preparation of Aryl Aldehydes, Ketones, and Nitriles

“…10 In connection with oxidative decarboxylation of aamino acids, it was reported the lead tetraacetate oxidation of their N-acyl derivatives gave N-acylimines which were hydrolyzed to the corresponding aldehydes. 5 As far as the transformation into nitriles is concerned, N-bromosuccinimide, 11 and alkaline bromine 12 have been employed as oxidizing agents. The isolated yields of nitriles obtained by these reactions, however, are only moderate.…”