A Novel Approach to the Efficient Oxygenation of Hydrocarbons under Mild Conditions. Superior Oxo Transfer Selectivity Using Dioxiranes

Abstract

The design of efficient and general methods for the selective oxyfunctionalization of unactivated carbon-hydrogen bonds continues to represent a major challenge for the community of chemists, despite the fact that the oxidation of alkanes is a major feature of the chemical economy. A low level of selectivity is characteristic of large-scale oxidation of hydrocarbons performed under customary industrial oxidizing conditions (e.g., the catalytic air oxidation of cycloalkanes); in these processes, selectivity is difficult to control, because they are often impacted by the usual problems associated with free-radical chain reactions. Thus, in the last decades much work has been devoted to the search for general methods of selective oxidation that could be applied to a variety of satured hydrocarbons. In this context, just a few leading methods appear encouraging at the present time. This Account addresses a new approach developed in our laboratory, consisting in the application of isolated dioxiranes, a class of powerful yet selective oxidants. We contend that the method shows promise to contribute resolution of a well-recognized general problem in the existing chemistry of alkanes, that is, to achieve efficient oxyfunctionalizations with high selectivity for simple as well as structurally complex targets.

Alcohols or Masked Alcohols as Directing Groups for C–H Bond Functionalization

“…Dioxirane-mediated CH oxidation has found important applications in organic synthesis. 35 In 2009, the Inoue group reported a hydroxylation of tertiary CH bonds directed by a removable trifluoromethyl dioxirane moiety that was derived from a free alcohol. This method allows construction of 1,3-diaxial diols in carbocyclic matrices.…”

“…35 The tertiary CH bond at the γ-position can be selectively oxidized with retention of stereochemistry (Scheme 26). The reactivity is affected by the three-dimensional orientation between the dioxirane and the γ-CH bond.…”

Applications of Chiral Three-membered Rings for Total Synthesis: A Review

“…The most efficient class of oxidants to perform the epoxidation of alkenes are dioxiranes [92]. In contrast to similar oxidizing agents, such as percarboxylic acids, the development of chiral dioxiranes for asymmetric epoxidations has met great success over the last decades [8,93].…”

Three‐Membered Heterocycles. Structure and Reactivity

“…For example, treatment of 2,3-dimethylbutane (840, Scheme 2.120) with 3-methyl-3-trifluoromethyldioxirane (841) (TFD) at low temperature results in rapid and almost quantitative conversion to tertiary alcohol 842 [816]. In general, tertiary sites are preferred to secondary, a phenomenon underscored by the oxidation of adamantane (843) with excess TFD, in which only tertiary sites are affected [817].…”