Palladium-catalyzed reactions of unactivated alkyl electrophiles

Bloome, Kayla Sue

Palladium-catalyzed reactions of unactivated alkyl electrophiles Public Deposited

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March 22, 2019

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Bloome, Kayla Sue
- Affiliation: College of Arts and Sciences, Department of Chemistry

Abstract

I. Palladium-Catalyzed Reactions of Unactivated Alkyl Electrophiles An overview of palladium-catalyzed reactions with sp3-hybridized electrophiles is presented. Cross-coupling reactions and carbonylations with alkyl halides and sulfonates are discussed in detail. II. Carbonylative Alkyl-Heck Type Cyclization of Alkyl Iodides A palladium-catalyzed carbonylative Heck-type cyclization of alkyl halides is described. Treatment of a range of primary and secondary alkyl iodides with catalytic palladium(0) under CO pressure forms a variety of synthetically versatile enone products. The reactivity described represents a rare example of a palladium-catalyzed Heck-type cyclization involving unactivated alkyl halides with β-hydrogens. Alkene substitution is well tolerated, and mono- and bicyclic carbocycles may be easily accessed. III. Alkyl-Heck Type Cyclizations of Alkyl Halides A palladium-catalyzed Heck-type reaction of unactivated alkyl iodides is described. This process displays broad substrate scope with respect to both alkene and alkyl iodide components and provides efficient access to a variety of cyclic products. The reaction is proposed to proceed via a hybrid organometallic-radical mechanism, facilitating the Heck-type process with alkyl halide coupling partners. IV. Palladium-Catalyzed Enantioselective Carbonylation of Alkyl Iodides A palladium-catalyzed enantioselective carbonylation of unactivated secondary alkyl iodides is reported. Preliminary results serve as proof-of-principle that hybrid radical-organometallic reactivity enables the stereoselective synthesis of α-chiral carbonyl compounds. V. Palladium-Catalyzed Ring Forming C-H Alkylations of Aromatic Systems A palladium-catalyzed intramolecular C-H alkylation of heteroarenes and arenes with unactivated alkyl halides is described. Preliminary results suggest this process is applicable to primary alkyl bromides and iodides and tolerates electron-rich and -poor aromatic systems. Our goal to be able to readily synthesize medium-ring fused aromatic structures so they can be readily applied to a variety of biologically active compounds.

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