Ethynylbenziodazolones (EBZ) as Electrophilic Alkynylation Reagents for the Highly Enantioselective Copper-Catalyzed Oxyalkynylation of Diazo Compounds |
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| Authors: | Dr Durga Prasad Hari Lionel Schouwey Verity Barber Dr Rosario Scopelliti Dr Farzaneh Fadaei-Tirani Prof Dr Jerome Waser |
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| Institution: | 1. Laboratory of Catalysis and Organic Synthesis, Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC LCSO, BCH 4306, 1015 Lausanne, Switzerland;2. Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC GE, BCH 2111, 1015 Lausanne, Switzerland |
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| Abstract: | Ethynylbenziodoxol(on)e (EBX) cyclic hypervalent iodine reagents are now established reagents for the alkynylation of radicals and nucleophiles, yet they present limited possibilities for further structure and reactivity modification. Herein, the first synthesis is reported for the corresponding ethynylbenziodazolone (EBZ) reagents, in which the oxygen atom in the iodoheterocycle is replaced by a nitrogen atom. The substituent on the nitrogen enables further fine-tuning of the reagent structure and reactivity. EBZ reagents are obtained easily from the corresponding benzamides by using a one-step procedure, and display reactivity comparable to that of EBX reagents. In particular, they are applied in an asymmetric copper-catalyzed oxyalkynylation of diazo compounds, which proceeds in high yield and enantioselectivity for a broad range of substituents on the diazo compounds and the alkyne. |
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| Keywords: | carbenes catalysis diazo compounds enantioselectivity hypervalent iodine |
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