Beilstein J. Org. Chem.2024,20, 162–169, doi:10.3762/bjoc.20.15
–Crafts reactions, rather than an oxocarbenium.
Keywords: 1-aryltetralines; Friedel–Crafts reaction; Hockrearrangement; oxidative cleavage; tandem reactions; Introduction
The Hock cleavage [1] consists in the acid-catalyzed rearrangement of organic hydroperoxides, leading to the oxidative cleavage of a
are excellent substrates for such reactions, affording electrophilic carbonyl derivatives susceptible to react with nucleophiles in the acidic reaction mixture [4][5][6][7][8]. Consequently, the Hockrearrangement is likely to be part of tandem processes involving this carbonyl function [9][10][11
rearrangement. Since the Hockrearrangement results in the formation of a molecule of water, we attempted to add a water scavenger to the reaction solution. Additives like molecular sieves 4 Å or Na2SO4 (2 equiv) did not show any improvement (Table 1, entry 3), while MgSO4 (2 equiv) had a stunning effect
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Graphical Abstract
Scheme 1:
The Hock rearrangement: (a) General mechanism (substituents are omitted); (b) Example of previous t...
Beilstein J. Org. Chem.2016,12, 1647–1748, doi:10.3762/bjoc.12.162
oxidation is widely used in organic synthesis for the preparation of esters and lactones and the Criegee reaction is applied to transform tertiary alcohols into ketones and aldehydes. The Hockrearrangement is a key step in the cumene (cumene–phenol) process and the Kornblum–DeLaMare is an important tool in
].
Carbonyl oxides (Criegee intermediates) are one of the most important compounds in tropospheric chemistry [309]. Direct investigations of formaldehyde oxide (CH2OO) or acetaldehyde oxide (CH3CHOO) reactions with water vapor, SO2, NO2 were carried out [310][311][312].
1.3 Hockrearrangement
The Hock
rearrangement is a protic or Lewis acid-promoted rearrangement of hydroperoxides A resulting in a C–C bond cleavage to form alcohol B and carbonyl compound C (Scheme 50) [313].
The Hockrearrangement is a key step in the cumene process, which is used for the industrial production of phenol (170) and acetone
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Graphical Abstract
Figure 1:
The named transformations considered in this review.