Alkynylation of Pentose Derivatives with Stereochemical Fidelity: Implications for the Regioselectivity of Alkynyl Diol Cycloisomerizations to Cyclic Enol Ethers
journal contributionposted on 2019-04-23, 16:50 authored by Frank E. McDonald, Dian Ding, Andrew J. Ephron, John Bacsa
This work characterizes a previously undetected epimerization in the preparation of alkynyl diols from pentose precursors utilizing the Ohira–Bestmann reagent. Lithium trimethylsilyldiazomethane (Colvin reagent) additions to the d-ribose and d-lyxose-derived benzylidene acetals provide the respective alkynyl diol stereoisomers, without epimerization. Regioselective tungsten-catalyzed cycloisomerizations of the d-ribose- and d-lyxose-derived alkynyl diols yield rigid bicyclic pyranose glycals, confirming the stereochemical fidelity of the Colvin alkynylation process.
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Stereochemical FidelityColvin alkynylation processstereochemical fidelityd-lyxose-derived benzylidene acetalsPentose Derivativesbicyclic pyranose glycalsLithium trimethylsilyldiazomethanealkynyl diolsd-riboseepimerizationColvin reagentd-lyxose-derived alkynyl diolspentose precursorsAlkynyl Diol CycloisomerizationsCyclic Enol Ethersalkynyl diol stereoisomersRegioselective tungsten-catalyzed cycloisomerizations