Oxidant controlled regio- and stereodivergent azidohydroxylation of alkenes via I₂ catalysis

Abstract

A novel, I2 catalyzed regio- and stereodivergent vicinal azidohydroxylation of alkenes leading to 1,2-azidoalcohols in high yields (up to 92%) and excellent dr (up to 98%) has been developed. This unprecedented transformation employs NaN3 and DMF as N- and O-nucleophiles respectively. The role of DMF as the O-source in the reaction has been unequivocally proven by (18)O labelling studies.

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

“…Notably, in the latter approach, copper‐based catalysts proved to be unsuccessful. Alternatively, iodine or Sn IV[17a] catalysis using organic peroxides have been employed towards azido alcohols, which, in turn, can then be oxidized to azidoketones with pyridiniumchlorochromate (PCC) …”

Regiodivergent and stereoselective hydroxyazidation of alkenes by biocatalytic cascades

“…Vicinal hydroxyazidation of alkenes offers a simpler and more convenient approach for preparing 1,2-azidoalcohols. So far, several effective approaches have been developed for the synthesis of 1,2-azidoalcohols through direct hydroxyazidation of alkenes ( Prasad et al., 2015 ; Sakurada et al., 2000 ). However, stoichiometric or excess oxidants must be used, and these methods are restricted by the specified O-sources.…”

Highly Diastereoselective Construction of Carbon– Heteroatom Quaternary Stereogenic Centers in the Synthesis of Analogs of Bioactive Compounds: From Monofluorinated Epoxyalkylphosphonates to α-Fluoro-, β-, or γ-Amino Alcohol Derivatives of Alkylphosphonates

“…The analysis of IR (band at 2,100 cm −1 ) (Hesse et al, 1997 ) as well as the 13 C NMR spectra of 36–39 confirmed the formation of tertiary azides. Thus, the signals of ( C- OH) carbon atoms were located around δ: 73–79 ( 3 J C−P 19–21 Hz) while signals of C N 3 appeared at δ: 57, similarly to 2-azido-2-phenylpropan-1-ol (Prasad et al, 2015 ). Although 3-hydroxyphosphonates 36–39 can rotate freely around the P-C1 and C1-C2 bonds, we would like to emphasize that in [D] chloroform they exist predominantly as their anti -conformers (arrangement of phosphonate and CH 2 OH moieties regarding C1-C2 bonds) as can be judged from the large (18–21 Hz) values of their 3 J C−P couplings together with the analysis of the NOESY and H-F HOESY spectra.…”