Tandem allylic alcohol isomerization/oxo-Michael addition reaction promoted by Re₂O₇

Abstract

Re2O7 enables a tandem allylic alcohol isomerization/oxa-Michael addition reaction of cyclohexadienone.

Synthesis and Morphology of AgReO4 Plates, Rods, and Stars

“…Rhenium in its highest oxidation state, Re +VII , is particularly interesting for catalysis and especially known as highly active catalyst for olefin metathesis reactions, oxo‐Michael additions, or deoxydehydration reactions . To this concern, Re 2 O 7 as well as (CH 3 )ReO 3 (methyltrioxorhenium, MTO) were most widely studied and are typically supported on micron‐sized particles as inert matrices (e.g.…”

“…To this concern, Re 2 O 7 as well as (CH 3 )ReO 3 (methyltrioxorhenium, MTO) were most widely studied and are typically supported on micron‐sized particles as inert matrices (e.g. Al 2 O 3 ) for use as heterogeneous catalyst . It turned out that the catalytic performance is significantly influenced by the supporting material .…”

“…Al 2 O 3 ) for use as heterogeneous catalyst . It turned out that the catalytic performance is significantly influenced by the supporting material . Surprisingly, Re +VII ‐containing nanoparticles that could be highly relevant for catalysis have been barely addressed by now.…”

Re2O7‐Mediated Dehydrative Cyclization Reactions: Total Synthesis of Herboxidiene and Its 12‐Desmethyl Analogue

“…We have been exploring [9] the use of Re 2 O 7 -catalyzed allylic alcohol transposition reactions [10] in complex molecule synthesis. These processes, in which allylic alcohols react with Re 2 O 7 to form allylic perrhenate esters that rearrange and cleave to form isomeric allylic alcohols, employ appended electrophiles to dictate the regioselectivity of the transposition reaction.…”

Re2O7‐Mediated Dehydrative Cyclization Reactions: Total Synthesis of Herboxidiene and Its 12‐Desmethyl Analogue

“…We have been exploring [9] the use of Re 2 O 7 -catalyzed allylic alcohol transposition reactions [10] in complex molecule synthesis.These processes,inwhich allylic alcohols react with Re 2 O 7 to form allylic perrhenate esters that rearrange and cleave to form isomeric allylic alcohols,e mploy appended electrophiles to dictate the regioselectivity of the transposi-tion reaction. However,w eo bserved [9c] that allylic alcohols can also serve as precursors to allylic cations (Scheme 1) during an investigation of epoxides as electrophilic traps.This result is consistent with calculations that show substantial charge separation in the transition states of perrhenate ester rearrangements [11] and with the generation of highly stabilized carbocations from allylic alcohols in bimolecular processes.…”