Abstract
The efficient generation of complex molecular architectures from simple precursors
is one of the most important aspects in the design and development of synthetic methodologies.
The chemistry of reactive species generated by the oxidative dearomatization of phenols,
such as o -quinone acetals, 6-acetoxycyclohexa-2,4-dienones, and their congeners, has stimulated
widespread interest among organic chemists, and the use of such reactive species has
emerged as a powerful method for the efficient synthesis of complex molecules. Our
approach to create molecular complexity and diversity involves the oxidative dearomatization
of 2-(hydroxymethyl)phenols to give spiro[cyclohexa-2,4-dienone-6,2′-oxiranes], followed
by cycloaddition and transformation of the resulting adducts in the ground and excited
states. In this account, we describe the evolution of the methodology and its application
which has led to the development of novel and efficient routes to a diverse array
of complex molecular architectures from simple aromatics.
1 Introduction
2 Cycloaddition of Cyclohexa-2,4-dienones of Types 3 and 4 and Manipulation of the Adducts in the Ground and Excited States
2.1 Cycloaddition of Cyclohexa-2,4-dienones of Types 3 and 4 : An Efficient Route to Functionalized and Appended Bicyclo[2.2.2]octanes
2.1.1 Cycloaddition of Cyclohexa-2,4-dienones of Types 3 and 4 with Electron-Deficient π-Partners
2.1.2 Cycloaddition of Cyclohexadienones of Type 4 with Vinyl Ethers and Vinyl Acetate
2.1.3 Cycloaddition of Cyclohexadienones of Types 3 and 4 with Acyclic 1,3-Dienes: Direct Entry to Bicyclo[2.2.2]octenones Having an endo -Vinyl Group
2.2 Manipulation of the Oxirane Moiety or the Chloromethyl and Hydroxy Groups in the
Adducts: Synthesis of Embellished Bicyclo[2.2.2]octanes
2.3 3,3-Sigmatropic Shift in Bicyclo[2.2.2]octanes: A General Stereoselective Route
to Functionalized cis -Decalin Derivatives
2.4 Sigmatropic Rearrangements of β,γ-Enones in Excited States: Stereoselective Routes
to Bicyclo[3.3.0]- and Bicyclo[4.2.0]octanes and Tricyclic Compounds
3 Synthetic Applications
3.1 Synthesis of Hirsutic Acid C and the Framework of Pupukeananes from a Common
Precursor
3.2 Chemistry of Fused Spiro[cyclohexa-2,4-dienone-6,2′-oxiranes] and Their Adducts:
Synthesis of Propellanes and Steroid–Polyquinane Hybrids
3.2.1 A General Route to [3.3.3]- and [4.3.3]Propellanes
3.2.2 Synthesis of Steroid–Polyquinane Hybrids
3.3 Synthesis of Tri- and Tetracyclic Networks of Atisane Diterpenoids
3.3.1 Synthesis of Tricyclo[6.2.2.01,6 ]dodecanes and Their Homologues
3.3.2 Synthesis of the Tetracyclic Network of Atisane Diterpenoids: An Interesting
Manifestation of Subtle Control by a Remote Functional Group
3.4 Intramolecular Cycloaddition of Cyclohexa-2,4-dienones: Synthesis of Platencin
4 Summary and Outlook
Key words oxidative dearomatizations - cyclohexa-2,4-dienones - cycloadditions - bicyclo[2.2.2]octanes
- photochemistry
