Mechanism of the reactions of alcohols with o-benzynes.

ABSTRACT: We have studied reactions of secondary and primary alcohols with benzynes generated by the hexadehydro-Diels-Alder (HDDA) reaction. These alcohols undergo competitive addition vs dihydrogen transfer to produce aryl ethers vs reduced benzenoid products, respectively. During the latter process, an equivalent amount of oxidized ketone (or aldehyde) is formed. Using deuterium labeling studies, we determined that (i) it is the carbinol C-H and adjacent O-H hydrogen atoms that are transferred during this process and (ii) the mechanism is consistent with a hydride-like transfer of the C-H. Substrates bearing an internal trap attached to the reactive, HDDA-derived benzyne intermediate were used to probe the kinetic order of the alcohol trapping agent in the H2-transfer as well as in the alcohol ad

SUBMITTER: Willoughby PH 

PROVIDER: S-EPMC4183651 | biostudies-literature | 2014 Oct

REPOSITORIES: biostudies-literature