Intramolecular Redox Processes Initiated by Hydride Shift - Yann Odabachian
This content explores intramolecular redox processes initiated by hydride shift, showcasing various applications, mechanisms, acceptors, donors, and transformations related to this chemical phenomenon. It delves into asymmetric transformations, hydride shifting on different alkynes, and more.
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Presentation Transcript
Intramolecular redox processes initiated by an hydride shift Yann Odabachian 25.09.2012
First type of application The tert-amino effect Thermic transformation : Lewis acid catalyzed : Review : Synthesis, 2006, 16, 2625
Other possibilities Room temperature hydride shift : Application to a functionalized molecule :
Transfer of an hydrogen atom on an asymetric center
Other type of hydride donor 1,5-Hydride shift from tertiary alkyl group : 1,6-Hydride shift from tertiary alkyl group
Imine as an hydride acceptor Using the tert-amino effect : Transfer from a benzylic position
Other types of acceptors : Unsaturated iminium : Aldehyde
Hydride shift on activated alkynes Fischer carbene substituted alkynes : Sulfone substituted alkynes :
Hydride shift on unactivated alkynes another pathway Different mechanism on conjugated alkynes
Hydride shift on unactivated alkynes another pathway Examples :
The Crabbe reaction Allene synthesis through a 1,5-Hydride Shift
Other possibilities : Access to disubstituted allenes
Trapping of a Crabbe reaction intermediate
Gold catalyzed cascade transformation involving a 1,5-Hydride Shift
Conclusion Development of efficient methods for the synthesis of various heterocycles (tetrahydroisoquinolines, ) Synthesis of allenes from easily availables starting materials
