Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 83, Issue 4, Pages 2198-2209Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.joc.7b03098
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Funding
- Sao Paulo Research Foundation (FAPESP) [2014/25770-6, 2013/07600-3, 2013/10639-9, 2016/18061-4]
- Brazilian National Research Council (CNPq) [157522/2015-6, 457027/2014-2]
- Coordination for the Improvement of Higher Education Personnel (PNPD-CAPES)
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Novel palladium-catalyzed redox-relay Heck arylation reactions of trisubstituted allylic alkenols were developed employing silyl and methyl ethers. The reactions proceeded under mild conditions in moderate to high yields in an excellent anti diastereoselectivity to form alpha,beta-disubstituted methyl ketones containing two contiguous stereocenters. The new redox-relay arylations using silyl and methyl ethers of the starting alkenols demonstrate that the presence of a free hydroxyl group is not a sine qua non condition for an effective redox-relay process as previously thought. Deuterium-labeled alkenols 2-d-10a, 2-d-10b, and 2-d-10c permitted tracking the palladium-hydride reinsertion steps in the conversion of the starting free alcohols, silyl, and methyl ethers into the corresponding methyl ketone 3-d-11a, with >98% deuterium retention. Moreover, the synthetic potential of the method was demonstrated with a straightforward synthesis of the meso-hexestrol in 4 steps, in 41% overall yield from alkenol 10a.
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