The ‘Ireland’ one-pot alcohol oxidation coupling reactions: celebrating 30 years of diverse synthesis

Abstract

In 1985, Robert Ireland and co-worker were devising synthetic routes to polyether ionophore antibiotics and during this process several highly reactive aldehydes were encountered, which made their isolation and subsequent elaboration difficult. To circumvent this problem, the synthetic route commenced from the alcohol which was oxidized to the aldehyde and, to the crude mixture, was added the nucleophile. This procedure, dubbed the 'Ireland' oxidative process was found to be highly successful and adapted by many research groups the world over. As we celebrate 30 years since this landmark discovery, the following review will take a journey of the most innovative and wonderful applications of this process.

(+)-Limonene Functionalization: Syntheses, Optimization, and Scale-up Procedures for Sustainable Polymer Building Blocks

“…Because ketones and aldehydes are valuable precursors in the synthesis of organic compounds, the Swern oxidation of the diols looked very promising. The advantage of this kind of oxidation lies on the fact that primary alcohols converted to aldehydes do not react any further to the corresponding carboxylic acids. , An additional plus in synthesis derives from the implementation of this oxidation in the Ireland approach, where unstable aldehydes react under one-pot conditions into important precursors for the pharmaceutical industry. In this report, both diols have been oxidized via Swern oxidations to yield the known short and long ketoaldehydes respectively, as represented in Figure .…”

“…16 Both (+)-limonene and Lim-CHO have been quantitatively converted into the short diol 21a,b and the long diol, respectively, 34 through a hydroboration−oxidation approach, which has been not only optimized for scale-up purposes but Both techniques yield the diamines with high yields and are optimized to be suitable for industrial applications, with the hydrogenation slightly ahead in terms of effectiveness and lack of byproducts. Alternatively, in Route B, a very effective protocol has been tuned and optimized for the Swern oxidation of the diols to yield the short 33 and long ketoaldehyde 34 in high yields and purity. The ketoaldehydes have been easily converted into their hitherto unknown short and long hydrazones that could be obtained quantitatively using the Dean−Stark technique.…”

Minimális fázisjelölés terc-butil csoporttal és alkalmazása Mitsunobu-, és Wittig-reakcióban

“…A Wittig reakció népszerűségét mutatja a napjainkban is megjelenő publikációk nagy száma. [58], [59], [60], [61], [62], [63], [64], [65], [66] Mindenképpen érdemes azonban megje- [69], [70], [71] Savas vagy bázikus funkciós csoportot tartalmazó olefinek esetében sóképzés [72] és/vagy pH változtatással járó extrakció alkalmazható a termék tisztítására. [73], [74], [75], [76], [77] Néhány esetben a Wittig reakció után a nyersterméket tisztítás nélkül alakítják tovább, majd egy későbbi lépésben, mikor a termék könnyebben elválasztható a foszfin-oxidtól végzik el a tisztítást.…”

Advances in the greener synthesis of chromopyrimidine derivatives by a multicomponent tandem oxidation process

“…Since its discovery, TOP has been employed in the synthesis of a wide range of useful materials from alcohols. In recent years, various oxidizing and nucleophilic compounds have been employed in TOP reactions 39 , 40 . Further, TOP has been extended to include multicomponent reactions (MCRs), enabling the synthesis of diverse valuable compounds 41 – 43 .…”