Recent Advances in Radical Dioxygenation of Olefins

Abstract

Dioxygenation of olefins is a valuable synthetic tool for the construction of 1,2‐diols and α‐oxygenated ketones. The use of radical approaches to achieve this direct 1,2‐difunctionalization has recently made considerable progress. The metal‐catalyzed reactions employ molecular oxygen and air as the oxidants, whereas metal‐free dioxygenation utilizes oxygen and peroxides. These oxidations are effective under mild conditions, with activated olefins found to be the most successful substrates. This microreview covers the recent developments in the radical dioxygenation of olefins, with respect to substrate scope, mechanism, and the advantages and disadvantages of the methods.

Visible‐Light‐Accelerated Copper(II)‐Catalyzed Regio‐ and Chemoselective Oxo‐Azidation of Vinyl Arenes

“…The use of visible-light photoredox catalysis has regained substantial attention during the last decade because of its operational simplicity for carrying out synthetic transformations in an environmentally benign and economic manner. [1,2] Photocatalysis,i np articular in combination with Cu I -based photoredox active complexes, [3] has become ap owerful tool for the difunctionalization [4] of carbon-carbon multiple bonds,p roviding an attractive alternative to thermal activation by transition-metal [5] or organic oxidants. [6] Organic azides, [7] especially azidoketones, [8,9] are valuable intermediates in organic synthesis,and consequently,various methods have been developed for their synthesis.T he most commonly used method is nucleophilic substitution [10] (Scheme 1), which requires pre-functionalized starting materials.…”

Manganese-Catalyzed Oxophosphorylation Reaction of Carbon–Carbon Double Bonds Using Molecular Oxygen in Air

“…TLC was performed on 0.25 mm E Merck silica gel 60 F254 plates. Diethyl (2-Oxo-2-(4-(trifluoromethyl)phenyl)ethyl)phosphonate (3k) 45) Yellow oil; 1…”

“…Chemical transformations using molecular oxygen as a reagent have attracted considerable attention from both industry and academia owing to its highly atom-economical, abundant, and environmentally friendly characteristics. [1][2][3][4][5] Among many transition metal-catalyzed aerobic chemical transformations, methodologies for directly incorporating oxygen into unactivated carbon-carbon double bonds, such as oxyazidation, 6) oxytrifluoromethylation, [7][8][9][10] oxysulfonylation, [11][12][13][14] oxysulfurization, [15][16][17] and dioxygenation, [18][19][20][21][22][23][24] remain highly desirable in synthetic chemistry.…”

Oxime radicals: generation, properties and application in organic synthesis

“…Stable N-oxyl radicals occupy a central place in organic chemistry as scavengers of C-centered radicals [9] and selective oxidation organocatalysts (for example, in the oxidation of alcohols to the corresponding carbonyl compounds [10,11]). Recently, highly reactive imidoxyl radicals (Figure 1, II) have found a wide application in the processes of hydrogen atom abstraction with cleavage of the C-H bond [12][13][14][15][16][17][18] and in the processes of functionalization of С=С double bonds [19,20]. Amidoxyl radicals (Figure 1, III) are applied in the functionalization of the double bonds [21][22][23][24][25][26] and in mild oxidations [27].…”