Course outline

Theme 1: Lithium Inorganics

Reductive Halogen – Li Exchange
C-Hal, C-H bond Metalation
Ar and HetAr Birch reduction

LiHal, LiCN and Related Salts
Li “salt effects” in Useful Synthetic Transformations
Survey of Li salts in Enolate, Grignard, Transition Metal Catalyzed Cross Coupling (Pd, Cu), Diels-Alder, Baylis-Hillman, and Elimination Reactions

LiOH, LiOOH, LiOR
Lactam, Lactone Ring Opening Reactions
Nondestructive Removal of Evans’ Chiral Auxiliary
Elimination, Substitution, C-N Coupling, Hunsdiecker Processes

Li amides
With and Beyond LDA. A Survey of Bases
For Deprotonation Reactions (Carbonyl Compounds, Alkynes, Epoxides)
Chiral Li Amides for Enantioselective Deprotonation
For Hydride Transfer Reaction

Theme 2: Lithio "Carbanions" (Polare Organometalle - Schlosser)

Li metal
Reductive Halogen – Li Exchange
C-Hal, C-H bond Metalation
Ar and HetAr Birch reduction

LiHal, LiCN and Related Salts
Li “salt effects” in Useful Synthetic Transformations
Survey of Li salts in Enolate, Grignard, Transition Metal Catalyzed Cross Coupling (Pd, Cu), Diels-Alder, Baylis-Hillman, and Elimination Reactions

LiOH, LiOOH, LiOR
Lactam, Lactone Ring Opening Reactions
Nondestructive Removal of Evans’ Chiral Auxiliary
Elimination, Substitution, C-N Coupling, Hunsdiecker Processes

Li amides
With and Beyond LDA. A Survey of Bases
For Deprotonation Reactions (Carbonyl Compounds, Alkynes, Epoxides)
Chiral Li Amides for Enantioselective Deprotonation
For Hydride Transfer Reaction

Theme 3: Lithio Enolates

Generation
Diversity of Enolate Structures
α-Li Carboxylic Acids and Related Derivatives
α-Li Aldehydes and Ketones. Major differences in Enolate Reactivity
α-Li Imines, Oximes, and Hydrazones
Survey of Lithio Enolate Reactions in Synthesis: Alkylation, Halogenation, Amination , Hydroxylation, Aldol, Michael, Claisen, and [2,3]-Wittig Rearrangement, inter alia
Emphasis on Enantioselective Methods

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Course Outline