C(sp3)-H oxygenation via alkoxypalladium(
In the present study of γ-C(sp3)-H acyloxylation of amine derivatives, a different mechanism was shown when tert-Bu hydroperoxide (TBHP) was used as an oxidant-namely, a bimetallic oxidative addition-oxo-insertion process. This catalytic model results in an alkoxypalladium(II) intermediate from which acyloxylation and alkoxylation products was formed. Exptl. and computational studies, including isolation of the putative post-oxo-insertion alkoxypalladium(II) intermediates, support this mechanistic model. D. functional theory revealed that the classical alkylpalladium(IV) oxidative addition pathway was higher in energy than the bimetallic oxo-insertion pathway. Further kinetic studies revealed second-order dependence on [Pd] and first-order on [TBHP], which was consistent with DFT anal. This procedure was compatible with a wide range of acids and alcs. for γ-C(sp3)-H oxygenation. Preliminary functional group transformations of the products underscore the great potential of this protocol for structural manipulation. In the experiment, the researchers used many compounds, for example, Tetrahydrofuran-2-carboxylic acid (cas: 16874-33-2Electric Literature of C5H8O3).
Tetrahydrofuran-2-carboxylic acid (cas: 16874-33-2) belongs to tetrahydrofuran derivatives. Tetrahydrofuran (THF) is a Lewis base that bonds to a variety of Lewis acids such as I2, phenols, triethylaluminum and bis(hexafluoroacetylacetonato)copper(II). THF (Tetrahydrofuran) is also used as a starting material for the synthesis of poly(tetramethylene ether) glycol (PTMG), etc.Electric Literature of C5H8O3
Referemce:
Tetrahydrofuran – Wikipedia,
Tetrahydrofuran | (CH2)3CH2O – PubChem