American Chemical Society
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Tetrahydrofuran Derivatives from Epoxides via Group Transfer Cyclization or Reductive Radical Cyclization of Organotellurium and Organoselenium Intermediates

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journal contribution
posted on 1997-01-10, 00:00 authored by Lars Engman, Vijay Gupta
Monosubstituted epoxides were regiospecifically ring-opened from the sterically least hindered side by benzenetellurolate and benzeneselenolate reagents to afford aryl β-hydroxyalkyl tellurides and selenides, respectively. These materials were O-allylated by treatment with allylic bromides/sodium hydride in tetrahydrofuran and O-prop-2-ynylated when reacted with propargyl bromide/sodium hydride. On photolysis in benzene containing 40 mol % of hexabutylditin, the β-(allyloxy)alkyl aryl tellurides were found to undergo group transfer cyclization to afford 2-substituted 4-[(aryltelluro)methyl]tetrahydrofurans (cis/trans = 1/3−1/10). The aryl β-(prop-2-ynyloxy)alkyl tellurides similarly afforded 2-substituted 4-[(aryltelluro)methylene]tetrahydrofurans with an E/Z-ratio close to unity. The β-(allyloxy)alkyl aryl selenides and aryl β-(prop-2-ynyloxy)alkyl selenides failed to undergo group transfer cyclization. In the presence of tributyltin hydride and 2,2‘-azobisisobutyronitrile, the former compounds were found to undergo reductive radical cyclization in high yields to afford 2-substituted 4-methyltetrahydrofurans (cis/trans = 1/3−1/10). Aryl β-(prop-2-ynyloxy)alkyl selenides similarly afforded 2-substituted 4-methylenetetrahydrofurans. 2-Alkoxy-2-(allyloxy)ethyl phenyl selenides, prepared by allyloxyselenenation of vinyl ethers, were found to undergo reductive radical cyclization to afford 2-alkoxy-4-methyltetrahydrofurans (cis/trans = 1/3−1/4). The preference for formation of trans-2,4-disubstituted tetrahydrofurans in the group transfer and reductive radical cyclizations was rationalized assuming a chairlike transition state with a preferred adoption of a pseudoequatorial position of the 2-substituent. By carrying out the reactions at lower temperatures (ambient or −45 °C), using triethylborane as an initiator, it was possible to further increase the trans selectivity in the reductive cyclizations.