Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 79, Issue 9, Pages 3937-3945Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jo500403q
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Funding
- German Research Foundation (DFG) [FR3418/1-1]
- Swiss National Science Foundation
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A method for the stereoselective synthesis of acyclic thioesters bearing adjacent quaternary and tertiary stereogenic centers under mild organocatalytic conditions was developed, alpha-Substituted monothiomalonates (MTMs) were used as thioester enolate equivalents. They reacted cleanly with nitroolefins in the presence of 1-6 mol % of cinchona alkaloid urea derivatives, and provided access to gamma-nitrothioesters with quaternary stereocenters in high yields and diastereo- and enantioselectivities. Mechanistic investigations provided insight into the parameters that determine the stereoselectivity and showed that the diastereoselectivity can be controlled by the nature of the MTM substrate. The different reactivities of the three functional groups (oxoester, thioester, nitro moieties) within the conjugate addition products allowed for straightforward access to other compounds with quaternary stereogenic centers, such as gamma-nitroaldehydes and gamma-butyrolactams.
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