β-Hydroxyimino Phosphorus Derivatives. An Efficient Tool in Organic Synthesis

Jesus      M. de los Santos; Javier      Vicario; Concepcion      Alonso; Francisco      Palacios

Abstract

The purpose of this review article is to illustrate synthetic aspects of functionalized phosphorus derivatives containing an oximo moiety at the beta-position. First section will be focused on the synthesis of phosphine oxides, phosphonates or phosphonium salts containing an oxime group. The synthesis of these derivatives comprises the carbon – phosphorus single bond construction by reaction of haloximes with phosphorus derivatives, nucleophilic addition of phosphorus reagents to carbonyl compounds, or nucleophilic addition of phosphorus reagents to nitro olefins. This section will also concentrate on the most practical routes for the synthesis of the target compounds, through carbon – nitrogen double bond formation, which are as follows: condensation processes of carbonyl compounds and hydroxylamine derivatives or addition of hydroxylamines to allenes or alkynes. The preparative use of beta-oximo phosphorus derivatives as synthetic intermediates will be discussed in a second section, comprising olefination reaction, oxidation of oximes to nitrile oxides by reaction at the C-N double bond of the oxime moiety, oxidation of these substrates to nitrosoalkenes, reduction to the corresponding hydroxylamines and some reactions at the hydroxyl group of the hydroxyimino moiety.

Keywords: β-Hydroxyimino phosphorus derivatives, α-haloximes, nitro olefins, nitrile oxides, nitrosoalkenes, Condensation Reaction, Olefination Reaction, Oxime Reductions, Nitrosoalkene Formation, Cyclization Reactions, Dehydratation of Oximes, O-Functionalization Reactions, diphenyl phosphine oxide (HPOPh2), fluoroalkyl p-toluenesulfonyl ketoximes, Grignard reagents