130669-72-6Relevant articles and documents
Synthesis of a Highly Functionalised and Homochiral 2-Iodocyclohexenone Related to the C-Ring of the Polycyclic, Indole Alkaloids Aspidophytine and Haplophytine
Dlugosch, Michael,Banwell, Martin G.
, p. 573 - 579 (2018)
The enzymatically-derived and enantiomerically pure (1S,2S)-3-bromocyclohexa-3,5-diene-1,2-diol (7) has been elaborated over 10 steps into cyclohexenone 8. The latter compound embodies the enantiomeric form of the C-ring associated with the hexacyclic framework of the alkaloid aspidophytine (2). As such, this work sets the stage for effecting the conversion of the enantiomeric metabolite ent-7 into compound ent-8, and thence, through previously established protocols, including a palladium-catalysed Ullmann cross-coupling reaction, into the title alkaloids.
A chemoenzymatic route to chiral siloxanes
Naoum, Ravi,Séguin, Jacqueline P.,Trant, John F.,Frampton, Mark B.,Hudlicky, Tomá?,Zelisko, Paul M.
, p. 4027 - 4031 (2016)
An approach employing two enzymes—toluene dioxygenase and immobilized lipase B from Candida antarctica (N435)—was explored as a potential biocatalytic method for the coupling of chiral diols with siloxane species. Analysis of reaction mixtures using1H NMR spectroscopy suggested that up to 66% consumption of the siloxane starting materials had occurred. Oligomeric species were observed and chiral products from the coupling of a cyclic diol with a siloxane molecule were isolated and characterized by MALDI-ToF MS and GPC. Immobilized lipases from Rhizomucor miehei and Thermomyces lanuginosus were also explored as potential catalysts for the coupling reactions, however, their use only returned starting material.
Chemoenzymatic Synthesis of the Antifungal Compound (–)-Pestynol by a Convergent, Sonogashira Construction of the Central Yne-Diene
Borra, Suresh,Kumar, Manoj,McNulty, James,Baidilov, Daler,Hudlicky, Tomas
, p. 77 - 79 (2019)
A total synthesis of the fungal-derived natural product pestynol is reported via a convergent chemoenzymatic approach from the readily available precursors geranyl bromide, ethyl acetoacetate, trimethylsilylacetylene, and bromobenzene. Synthetic (–)-pestynol proved to be identical in all respects to the natural material, allowing confirmation of the structure including absolute stereochemistry.
Chemoenzymatic and Enantiomeric Switching Regimes Enabling the Synthesis of Homochiral Cyclohexa-2,5-dienones Incorporating All-Carbon Quaternary Centers
Ye, Sebastian,Banwell, Martin G.
, p. 15403 - 15412 (2021/10/25)
The enantiomerically pure, bromobenzene-derived metabolite 5 has been transformed into enone 20 using a reaction sequence involving Suzuki-Miyaura cross-coupling and Eschenmoser-Claisen rearrangement processes. Treatment of compound 20 with lithium hydroxide results in an acetonide fragmentation reaction that delivers the 4,4-disubstituted cyclohexa-2,5-dienone 21, reductive de-oxygenation of which leads to congener 22. A closely related sequence of reactions can be used to convert the same homochiral starting material 5 into compound ent-22.
The Synthesis of Certain Phomentrioloxin A Analogues and Their Evaluation as Herbicidal Agents
Taher, Ehab S.,Guest, Prue,Benton, Amanda,Ma, Xinghua,Banwell, Martin G.,Willis, Anthony C.,Seiser, Tobias,Newton, Trevor W.,Hutzler, Johannes
, p. 211 - 233 (2017/04/26)
A series of 28 analogues of the phytotoxic geranylcyclohexentriol (-)-phomentrioloxin A (1) has been synthesized through cross-couplings of various enantiomerically pure haloconduritols or certain deoxygenated derivatives with either terminal alkynes or borylated alkenes. Some of these analogues display modest herbicidal activities, and physiological profiling studies suggest that analogue 4 inhibits photosystem II in isolated thylakoids in vitro.