40790-56-5Relevant articles and documents
Electrochemically driven desaturation of carbonyl compounds
Gnaim, Samer,Takahira, Yusuke,Wilke, Henrik R.,Yao, Zhen,Li, Jinjun,Delbrayelle, Dominique,Echeverria, Pierre-Georges,Vantourout, Julien C.,Baran, Phil S.
, p. 367 - 372 (2021/03/31)
Electrochemical techniques have long been heralded for their innate sustainability as efficient methods to achieve redox reactions. Carbonyl desaturation, as a fundamental organic oxidation, is an oft-employed transformation to unlock adjacent reactivity through the formal removal of two hydrogen atoms. To date, the most reliable methods to achieve this seemingly trivial reaction rely on transition metals (Pd or Cu) or stoichiometric reagents based on I, Br, Se or S. Here we report an operationally simple pathway to access such structures from enol silanes and phosphates using electrons as the primary reagent. This electrochemically driven desaturation exhibits a broad scope across an array of carbonyl derivatives, is easily scalable (1–100 g) and can be predictably implemented into synthetic pathways using experimentally or computationally derived NMR shifts. Systematic comparisons to state-of-the-art techniques reveal that this method can uniquely desaturate a wide array of carbonyl groups. Mechanistic interrogation suggests a radical-based reaction pathway. [Figure not available: see fulltext.]
Acceptorless dehydrogenation of C-C single bonds adjacent to functional groups by metal-ligand cooperation
Kusumoto, Shuhei,Akiyama, Midori,Nozaki, Kyoko
supporting information, p. 18726 - 18729 (2014/01/06)
Unprecedented direct acceptorless dehydrogenation of C-C single bonds adjacent to functional groups to form α,β-unsaturated compounds has been accomplished by using a new class of group 9 metal complexes. Metal-ligand cooperation operated by the hydroxycyclopentadienyl ligand was proposed to play a major role in the catalytic transformation.
Oxidative allylic rearrangement of cycloalkenols: Formal total synthesis of enantiomerically pure trisporic acid B
Dubberke, Silke,Abbas, Muhammad,Westermann, Bernhard
, p. 421 - 425 (2011/06/11)
Enantiomerically highly enriched unsaturated β-ketoesters bearing a quaternary stereocenter can be utilized as building blocks for the synthesis of natural occurring terpenes, i. a., trisporic acid and its derivatives. An advanced building block has been
