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Enantioselective synthesis of highly oxygenated acyclic quaternary center-containing building blocks via palladium-catalyzed decarboxylative allylic alkylation of cyclic siloxyketones.

ABSTRACT: The development of a palladium-catalyzed enantioselective decarboxylative allylic alkylation of cyclic siloxyketones to produce enantioenriched silicon-tethered heterocycles is reported. The reaction proceeds smoothly to provide products bearing a quaternary stereocenter in excellent yields (up to 91% yield) with high levels of enantioselectivity (up to 94% ee). We further utilized the unique reactivity of the siloxy functionality to access chiral, highly oxygenated acyclic quaternary building blocks. In addition, we subsequently demonstrated the utility of these compounds through the synthesis of a lactone bearing vicinal quaternary-trisubstituted stereocenters.

SUBMITTER: Ngamnithiporn A

PROVIDER: S-EPMC8162308 | biostudies-literature | 2020 Sep

REPOSITORIES: biostudies-literature

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Enantioselective synthesis of highly oxygenated acyclic quaternary center-containing building blocks <i>via</i> palladium-catalyzed decarboxylative allylic alkylation of cyclic siloxyketones.

Ngamnithiporn Aurapat A Iwayama Toshihiko T Bartberger Michael D MD Stoltz Brian M BM

Chemical science 20200915 40

The development of a palladium-catalyzed enantioselective decarboxylative allylic alkylation of cyclic siloxyketones to produce enantioenriched silicon-tethered heterocycles is reported. The reaction proceeds smoothly to provide products bearing a quaternary stereocenter in excellent yields (up to 91% yield) with high levels of enantioselectivity (up to 94% ee). We further utilized the unique reactivity of the siloxy functionality to access chiral, highly oxygenated acyclic quaternary building b ...[more]

PMID: 34123197

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