Catalytic Electrophilic Amination Reactions

Berman, Ashley M.

Catalytic Electrophilic Amination Reactions Public Deposited

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March 20, 2019

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Berman, Ashley M.
- Affiliation: College of Arts and Sciences, Department of Chemistry

Abstract

Chapter One: Copper-Catalyzed Electrophilic Amination of Organozinc Nucleophiles The copper-catalyzed electrophilic amination of diorganozinc reagents using Obenzoyl hydroxylamines as electrophilic nitrogen sources has been developed. Simple and functionalized aryl-, heteroaryl-, benzyl, n-alkyl-, s-alkyl-, and t-alkyl nucleophiles couple with R2NOC(O)Ph and RHNOC(O)Ph reagents in the presence of catalytic quantities of copper salts to provide tertiary and secondary amines, respectively, in generally good yields. In many cases the product may be isolated analytically pure after a simple extractive workup. The amination process is shown to tolerate a significant degree of steric demand. The amination of nominally unreactive Caryl-H bonds via a sequential directed ortho metalation/transmetalation/catalytic amination reaction sequence is detailed. The direct Cu-catalyzed amination of Grignard reagents using cocatalysis by ZnCl2 is described. Chapter Two: Nickel-Catalyzed Electrophilic Amination of Organozinc Nucleophiles The nickel-catalyzed electrophilic amination of organozinc halides using Obenzoyl hydroxylamines has been developed. Simple and functionalized aryl-, benzyl, and n-alkyl- nucleophiles couple with R2NOC(O)Ph reagents in the presence of catalytic quantities of Ni(PPh3)2Cl2 to provide tertiary amines in generally good yields. The reaction is noteworthy for the mild reaction conditions employed and the ease of product purification (acid/base extractive work-up). Chapter Three: Electrophilic Amination of o-Nitrobenzyl Silanes The electrophilic amination of o-nitrobenzyl silanes using di-tert-butyl azodicarboxylate as electrophilic nitrogen source and catalytic tetrabutylammonium fluoride as activator has been developed. A wide variety of á-alkyl and 4’- substituted onitrobenzyl silanes couple with di-tert-butyl azodicarboxylate in the presence of catalytic quantities of tetrabutylammonium fluoride to provide N-benzyl hydrazides in good yields.

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