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Full-Text Articles in Physical Sciences and Mathematics
One-Pot Reactions Of Ethyl Propiolate, Ana Maria Neferu
One-Pot Reactions Of Ethyl Propiolate, Ana Maria Neferu
Honors Theses
Through an efficient one-pot reaction sequence, ethyl propiolate can be transformed into a complex, usefully functionalized bicyclic product. Thioconjugate addition yielding Z-selective enoates has been developed for both aromatic thiols (trialkylamine-catalyzed) and aliphatic thiols (KOt-Bu-catalyzed). The oxidation of the thioenoates thus generated is followed by Li-catalyzed oxidation to sulfones using mCPBA, and Li-catalyzed Diels–Alder addition of cyclopentadiene. These subsequent steps are performed in situ, without any purification of intermediates. The yields obtained using the described synthesis are acceptable for a one-pot three-step sequence. Preliminary conjugate addition results with alcohols and amines as nucleophiles are also presented.
One-Pot Synthesis Of (Z)-B-Sulfonyl Enoates From Ethyl Propiolate, C. Wade Downey, Smaranda Craciun, Ana M. Neferu, Christina A. Vivelo, Carly J. Mueller, Brian C. Southall, Stephanie Corsi, Eric W. Etchill, Ryan J. Sault
One-Pot Synthesis Of (Z)-B-Sulfonyl Enoates From Ethyl Propiolate, C. Wade Downey, Smaranda Craciun, Ana M. Neferu, Christina A. Vivelo, Carly J. Mueller, Brian C. Southall, Stephanie Corsi, Eric W. Etchill, Ryan J. Sault
Chemistry Faculty Publications
B-Sulfonyl enoates may be synthesized through a one-pot two-step sequence from ethyl propiolate with good to excellent selectivity for the Z isomer. Trialkylamines catalyze thioconjugate additions of aryl thiols, and alkoxides catalyze the addition of aliphatic thiols. Addition of meta-chloroperbenzoic acid (mCPBA) and LiClO4 to the reaction mixture provides rapid access to the sulfonyl enoates. Yields of the pure Z isomer range from 51 – 90%.
One-Pot Three-Step Thioconjugate Addition-Oxidation-Diels–Alder Reactions Of Ethyl Propiolate, C. Wade Downey, Smaranda Craciun, Christina A. Vivelo, Ana M. Neferu, Carly J. Mueller, Stephanie Corsi
One-Pot Three-Step Thioconjugate Addition-Oxidation-Diels–Alder Reactions Of Ethyl Propiolate, C. Wade Downey, Smaranda Craciun, Christina A. Vivelo, Ana M. Neferu, Carly J. Mueller, Stephanie Corsi
Chemistry Faculty Publications
Ethyl propiolate undergoes one-pot three-step thioconjugate addition-oxidation-Diels–Alder cycloaddition when treated with a variety of thiols in the presence of catalytic base, meta-chloroperbenzoic acid, lithium perchlorate, and cyclopentadiene. The reaction of S‑aryl thiols is catalyzed by trialkylamines, and the reaction of aliphatic thiols requires catalytic alkoxide base. Yields of the major diastereomer of the conveniently functionalized bicyclic products range from 47 to 81% depending upon the thiol reactant, which compares favorably to yields observed when the entire synthesis is performed step by step.