Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, USA.
J Org Chem. 2012 Jan 20;77(2):825-42. doi: 10.1021/jo202314a. Epub 2012 Jan 3.
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.
人工模拟萜类生物合成的环化阶段激发了新方法的发明，因为使用含有最小功能的碳骨架限制了化学家合成策略的工具包。例如，从五碳构建块构建萜烯骨架将是实验室中令人兴奋的模拟途径。自然界会将 γ,γ-二甲基烯丙基焦磷酸（DMAPP）和异戊烯焦磷酸（IPP）齐聚、环化，然后氧化成所有已知的萜类化合物。从异戊二烯开始，这项工作的目标是模拟自然界快速构建分子复杂性的方法。原则上，异戊二烯的可控齐聚将极大地简化医药、香水、香料和材料行业中使用的萜类化合物的合成。本文阐述了我们通过零价镍催化，借鉴 Wilke 及其同事的经典研究，以可控方式将异戊二烯或丁二烯与炔烃冷聚合的广泛努力。
