An approach to mimicking the sesquiterpene cyclase phase by nickel-promoted diene/alkyne cooligomerization.
Artificially mimicking the cyclase phase of terpene biosynthesis inspires the invention of new methodologies, since working with carbogenic frameworks containing minimal functionality limits the chemist's toolbox of synthetic strategies. For example, the construction of terpene skeletons from five-carbon building blocks would be an exciting pathway to mimic in the laboratory. Nature oligomerizes, cyclizes, and then oxidizes γ,γ-dimethylallyl pyrophosphate (DMAPP) and isopentenyl pyrophosphate (IPP) to all of the known terpenes. Starting from isoprene, the goal of this work was to mimic Nature's approach for rapidly building molecular complexity. In principle, the controlled oligomerization of isoprene would drastically simplify the synthesis of terpenes used in the medicine, perfumery, flavor, and materials industries. This article delineates our extensive efforts to cooligomerize isoprene or butadiene with alkynes in a controlled fashion by zerovalent nickel catalysis building off the classic studies by Wilke and co-workers.
Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, USA.
Dane
D
Holte
Daniel C G
DC
Götz
Phil S
PS
Baran
D000480:Alkynes / Q000138:chemical synthesis / Q000737:chemistry*; D002070:Butadienes / Q000737:chemistry*; D019755:Carbon-Carbon Lyases; D002384:Catalysis; D060326:Chemistry Techniques, Synthetic / Q000379:methods*; D045782:Hemiterpenes / Q000737:chemistry*; D018716:Molecular Mimicry; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry*; D010420:Pentanes / Q000737:chemistry*
D000480:Alkynes; D002070:Butadienes; D045782:Hemiterpenes; D010420:Pentanes; C005059:isoprene; D009532:Nickel; D019755:Carbon-Carbon Lyases; C051130:trichodiene synthetase