Total Synthesis of (+)‐Aquaticol by Biomimetic Phenol Dearomatization: Double Diastereofacial Differentiation in the Diels–Alder Dimerization of Orthoquinols with a C₂‐Symmetric Transition State

Abstract

The absolute configuration of (þ)-aquaticol (1 a) described in this Communication should be revised to 3S,10S,14R,23R as shown on the structure below and its accompanying ORTEP diagram (monoclinic, P2 1 , Flack factor = À0.2(2), CCDC-295794). (þ)-Aquaticol was derived from SIBX-mediated oxidation of (þ)-(R)-hydroxycuparene (3). We thank Professor John Porco and Suwei Dong (Boston University) for pointing out this issue.

Oxidative Dearomatization of Phenols: Why, How and What For?

“…We carried out a DFT search of all transition states (TSs) experimentally leading to the eight endo-cyclodimers from the four ortho-quinols, including 117 and 118, derived from rac-116. 136 These calculations indicated that these TSs are asynchronous with an initial formation of the C 5 -C 5¢ bond. Most remarkably, the TS-94 structure that leads to dimer 94 displays a twofold axis of symmetry (Figure 7), so that it is not possible to differentiate the diene from the dienophile at the TS level.…”

Chemistry of Polyvalent Iodine

“…The synthetic utility of SIBX has been demonstrated on the reactions of hydroxylative phenol dearomatization,418,960,961 oxidation of sulfides into sulfoxides,962 oxidative demethylation of phenolic methyl aryl ethers,959 and other useful oxidative transformations 959…”

Site‐selective Oxidative Dearomatization of Phenols and Naphthols into ortho‐Quinols or Epoxy ortho‐Quinols using Oxone as the Source of Dimethyldioxirane

“…If we consider the oxidative dearomatization of phenol 1 a with oxaziridines or hypervalent iodine reagents–– (Scheme a), only the cyclodimer 3 a was obtained. When the reaction of 1 a is performed with Oxone/NaHCO 3 /CH 3 CN, as source of singlet oxygen ( 1 O 2 ), followed by reduction with Na 2 S 2 O 3 , the para ‐quinol 4 a was formed (Scheme b) .…”