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.
Highlights
Silicon-containing hetereocycles are an important class of organic molecules o en used in the context of temporary functional groups in the synthesis of natural products and drug molecules.[1]
We believe that utilization of the silicon functionality in the alkylation products would allow for the synthesis of enantioenriched acyclic quaternary stereocenters, a motif that still poses a signi cant challenge in organic synthesis.[9]
With the substrates in hand, our studies continued with an investigation of the palladium-catalyzed decarboxylative allylic alkylation (Table 1)
Summary
Silicon-containing hetereocycles are an important class of organic molecules o en used in the context of temporary functional groups in the synthesis of natural products and drug molecules.[1]. Scheme 1 Enantioselective synthesis of cyclic siloxanes. An enantioselective method to access cyclic siloxanes bearing all-carbon quaternary stereocenters has not been reported to date.
Sign-in/Register to view highlights & summary Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
