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Regioselective Intramolecular Carbon-Hydrogen Insertion in Copper-Catalyzed Carbenoid Decompositions of cis-1-Methyl-3-Arylcyclohexane-1-Diazomethyl Ketones : Some Synthetic Applications
Authors:Sephali Chakrabarty  Jayanta K Ray  Debabrata Mukherjee  Usha R Ghatak
Institution:Department of Organic Chemistry , Indian Association for the Cultivation of Science , Jadavpur, Calcutta, 700032, India
Abstract:Recently, we have developed1 a new route for the stereo-specific introduction of an angular carboxyl or functionalized methyl groups2 in a rigid hydrophenanthrene moiety. The key step in this approach is a regioselective intramolecular α-keto carbenoid insertion across the benzylic C-H bond (at C-4a) in CuSO4-catalyzed thermal decomposition of the diazoketones  /></span> and <span class= /></span> to the corresponding tetracyclic ketones <span class= /></span> and <span class= /></span> in moderate to good yields. A modified procedure<sup>3</sup> of carbenoid decomposition of these diazoketones, in the presence of Cu<sub>2</sub>O under irradiation with tungsten filament lamp, improves the yields of the desired C-H insertion products. Thus, the ketones <span class= /></span> and <span class= /></span> have been prepared now in consistently higher yields (53-55%) from the pure diazoketones <span class= /></span>, m.p. 125-127°, and <span class= /></span>, m.p.</td>
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