Recent Advances on Catalytic Osmium‐Free Olefin syn‐Dihydroxylation

Abstract

The syn‐dihydroxylation of olefinic group is one of the most important synthetic transformations which leads to the controlled formation of syn‐diol. Such 1,2‐diol structure is integrated into more complex architectures and substantially participates in the development of biologically active molecules and other fine chemicals. This minireview describes recent evolution of this research field in the past decade, surveying osmium‐free and more eco‐compatible system and in particular the direct oxidation of olefins catalyzed by transition metal complexes.

Nonheme Iron-Catalyzed Enantioselective cis -Dihydroxylation of Aliphatic Acrylates as Mimics of Rieske Dioxygenases

“…[3][4][5][6][7] With respect to their distinct structural features and significant roles in synthetic organic chemistry, diverse methodologies have been developed to gain access to enantiopure syn-2,3dihydroxy esters. [8][9][10][11][12][13][14][15][16][17][18][19] To this end, enantioselective cis-dihydroxylation of , -unsaturated esters represents the most efficient and straightforward strategy for the synthesis of syn-2,3-dihydroxy esters. These include metalcatalyzed (Mn, 15 Ru, 16 Os 1 and Pd 17,18 ) and organocatalyzed 19 enantioselective cis-dihydroxylation with various oxidants.…”

Seeing the cis-Dihydroxylating Intermediate: A Mononuclear Nonheme Iron-Peroxo Complex in cis-Dihydroxylation Reactions Modeling Rieske Dioxygenases

“…Inspired by the iron-dependent arene cis -dihydroxylating Rieske dioxygenases, synthetic nonheme iron complexes have been extensively explored as catalysts for the cis -dihydroxylation of olefins using hydrogen peroxide (H 2 O 2 ) as a terminal oxidant, to replace the toxic and expensive osmium (and related high-valent compounds with cis -dioxo groups) catalyzed cis -dihydroxylation of olefins . As a result, several landmark discoveries, pioneered by Que, Che, and Costas, were observed in the nonheme iron-catalyzed (asymmetric) cis -dihydroxylation of olefins by H 2 O 2 . − Regarding the cis -dihydroxylating intermediate, an iron­(V)-oxo-hydroxo (HO-Fe V O) species, which is the product of the O–O bond heterolysis of an iron­(III)-hydroperoxo intermediate, has been proposed as the active cis -dihydroxylating intermediate responsible for the cis -dihydroxylation of olefins in biomimetic systems (Figure S1b); ,,, in several cases, other iron–oxygen intermediates, such as iron­(III)-superoxo and iron­(III)-hydroperoxo, have been proposed as a potent oxidant in the cis -dihydroxylation reactions. ,, Accordingly, reaction mechanisms were proposed with an assumption that an HO-Fe V O species is the cis -dihydroxylating intermediate that reacts with olefins to yield cis -diols (Figure S1b).…”

Synthesis and Applications of Periodate for Fine Chemicals and Important Pharmaceuticals

“…Recent computational studies indicate a noninnocent role of periodate in the oxidative cyclization of 1,5-dienes, which too could affect other reactions . The emerging aldehydes are usually oxidized to carboxylic acids, but recent developments enable the halt of the oxidation at this or the diol stage. − The cleavage of alkynes to aldehydes, , and the oxidative cyclization of dienes are further important innovations, , as well as the immobilization of the ruthenium on composite materials, or on silica. , The application of ruthenium catalysts in natural product synthesis has been reviewed thoroughly. − …”