Regio- and Stereoselective Addition of HO/OOH to Allylic Alcohols

Abstract

A range of allylic alcohols are shown to readily react with ethereal H2O2 in the presence of catalytic amounts of Na2MoO4-gly or MoO2(acac)2, affording the CC trans hydroxylation–hydroperoxylation products in good yields with high regio- and stereoselectivity. Use of enantiomers of cyclic substrates resulted in corresponding enantiopure diol-tert-hydroperoxides. The possibility of further conversion of the diol-tert-hydroperoxides into triols or linear building blocks with an isolated tert-peroxy group containing a quaternary center is also exemplified.

Non-covalent interactions of the hydroperoxo group in crystalline adducts of organic hydroperoxides and their potassium salts

“…located from a difference Fourier map with all parameters refined) hydrogen atoms of hydroperoxide groups. 30,[49][50][51][52][53] Herein, cocrystals of organic hydroperoxides are classified as adducts if only H-bond (HB-D and/or HB-A) interaction between coformer and organic hydroperoxide occurs. In almost all cases, HB-D is implemented as H-bonds with coformers.…”

Enantioselective Synthesis Muqubilin and Negombatoperoxides B and C/D

“…In connection with the study of hydroxyhydroperoxidation of allylic alcohols, we recently developed a convenient access 10 to chiral building blocks with an isolated hydroperoxy groupcontaining quaternary center of predeterminable absolute configuration, which are present in a myriad of natural cyclic peroxides. To illustrate the potential of such building blocks in synthesis and structural/configurational assignment those natural peroxides, we embarked on an enantioselective syntheses described below.…”

“…25 The construction of 2 used essentially the same strategy for its counterpart in 1. However, use of ent-5 as the starting material (Scheme 7) through the same procedure 10 for preparation of 6 gave ent-6. 26 The remaining steps were performed as described above for the synthesis of 14 in comparable yields.…”

“…The dry THF and CH 2 Cl 2 in air/moisture-sensitive experiments were of the “99.9%, SuperDry” grade. H 2 O 2 -saturated Et 2 O (ethereal hydrogen peroxide) was prepared as described before. Column chromatography was performed on silica gel (300–400 mesh) under slightly positive pressure.…”

“…Removal of the drying agent by filtration and rotary evaporation of the filtrate gave a crude oil, which was purified by column chromatography (20:1 PE/EtOAc) on silica gel to afford 7 as a colorless oil (6.5 g, 14.9 mmol, 87%). Methyl-(S,E)-4-((tert-butyldimethylsilyl)peroxy)-4-methyl-8-((triisopropylsilyl)oxy)oct-2-enoate (10). A solution of DMSO (3.2 mL, 44.4 mmol) in dry CH 2 Cl 2 (10 mL) was added very slowly to a solution of (COCl) 2 (2.8 mL, 33.3 mmol) in dry CH 2 Cl 2 (60 mL) stirred at −78 °C under argon (balloon).…”