74852-25-8Relevant academic research and scientific papers
Regioselective and Stereospecific Copper-Catalyzed Deoxygenation of Epoxides to Alkenes
Yu, Jingxun,Zhou, Yu,Lin, Zhenyang,Tong, Rongbiao
supporting information, p. 4734 - 4737 (2016/09/28)
Two copper salts (Cu(CF3CO2)2 and IMesCuCl) were identified as earth-abundant, inexpensive, but effective metal catalysts together with diazo malonate for chemo-/regioselective and stereospecific deoxygenation of various epoxides with tolerance of common functional groups (alkene, ketone, ester, p-methoxybenzyl, benzyl, tert-butyldimethylsilyl, and triisopropylsilyl). In particular, the unprecedented regioselectivity allowed for the first time monodeoxygenation of diepoxides to alkenyl epoxides. Density functional theory mechanistic studies showed that the deoxygenation occurred by collapsing the free ylide, unfavoring the possible intuitive pathway via cycloreversion of possible oxetane.
Transition-metal Mediated Asymmetric Synthesis. Part 3. Preparation and Stereospecific Alkylation of Unsymmetrically Substituted Tricarbonyl(cyclohexadienyl)iron(1+) Salts: an Organometallic Approach to the Synthesis of Carvone, Cryptomerion, and Bilobanone
Stephenson, G. Richard
, p. 2449 - 2456 (2007/10/02)
Tricarbonyl(η5-3-methoxy-2-methylcyclohexa-2,4-dienyl)iron(1+)hexafluorophosphate(1-) has been prepared by a novel method based on thallium(III) oxidation.The opposite substitution pattern is obtained by hydride abstraction.Alkylation by bis(1-methylethenyl)cadmium, to introduce an olefinic side-chain, has been shown to be stereospecific for the α-face, and removal of the metal affords the expected enones. (+/-)-Carvone and -sylve-carvone have been prepared by this means.The results indicate the importance of regiocontrol of alkylation if chiral salts are to be employed in synthesis.
