Vicinal anti‐Dioxygenation of Alkenes

Abstract

Vicinal diols and their derivatives are common motifs in al arge number of biologically active compounds and are also important intermediates in organics ynthesis. To achieve these structural units in ah ighly stereoselective manner,d irect dioxygenation of simple alkene precursors has provedt ob et he most straightforward approach, and thus many practical proceduresu sing various strategies have been developed. In this Focus Review ac oncise summary of the main methods for anti-dioxygenation of olefins is presented. Scheme1.Categories of vicinal anti-dioxygenation of alkenes.[a] Prof.Scheme6.Ammonium-directed formal anti-dioxygenation as key step for the synthesis of aza-and amino sugars.Scheme7.N-Oxide-directed formal anti-dihydroxylation.Scheme8.NafionN R50-catalyzed anti-dihydroxylation.Scheme9.PTSA-catalyzed anti-dihydroxylation.Scheme14. SeO 2 -catalyzed anti-dihydroxylation.Scheme15. Diselenide-catalyzed anti-dihydroxylationo fcyclohexene.Scheme16. Chiral-diselenide-catalyzed asymmetric anti-dihydroxylation.

Sigma-bond activation reactions induced by unsaturated Os(IV)-hydride complexes

“…However, in general, the resultant reduced metallic species cannot be reoxidized by molecule oxygen but require strong oxidants. 85 Given the advantages of air or dioxygen as final oxidant, the metal-promoted activation of the O 2 molecule is a reaction of great interest.…”

On-demand, in situ, generation of ammonium caroate (peroxymonosulfate) for the dihydroxylation of alkenes to vicinal diols

“…This can be achieved by the reaction of the alkene with a reactive oxidant to generate an epoxide intermediate, that can undergo ring-opening under acidic or basic conditions to the diol (Scheme 1). 2,3 In principle, O 2 gas is the ideal oxidant in terms of its availability, atom economy and sustainability. However, implementation of aerobic processes can have unique challenges, not least of all, the management of solubility and flammability limits of O 2 gas in organic solvents.…”

“…This can be achieved by the reaction of the alkene with a reactive oxidant to generate an epoxide intermediate, that can undergo ring-opening under acidic or basic conditions to the diol (Scheme 1). 2,3…”

Photo‐Induced Dihydroxylation of Alkenes with Diacetyl, Oxygen, and Water

“…Dihydroxylation of alkenes offers a straightforward access to 1,2-diols. [1][2][3][4][5] Osmium tetroxide is often utilized as a catalyst for direct dihydroxylation despite of its high toxicity (Scheme 1,a). Asymmetric variants of the osmium-catalyzed reaction are also available.…”