2-Azadienes as Enamine Umpolung Synthons for the Preparation of Chiral Amines

Abstract

The development of new strategies for the preparation of chiral amines is an important objective in organic synthesis. In this Synpacts, we summarize our approach for catalytically accessing nucleophilic aminoalkyl metal species from 2-azadienes, and its application in generating a number of important but elusive chiral amine scaffolds. Reductive couplings with ketones and imines afford 1,2-amino tertiary alcohols and 1,2-diamines, respectively, whereas fluoroarylations of gem-difluoro-2-azadienes deliver α-trifluoromethylated benzylic amines.1 Introduction2 Background: Umpolung Strategies for Preparing Chiral Amines3 Background: 2-Azadienes4 Reductive Couplings of 2-Azadienes5 Fluoroarylations of gem-Difluoro-2-azadienes6 Summary and Outlook

A Diastereodivergent and Enantioselective Approach to syn- and anti-Diamines: Development of 2-Azatrienes for Cu-Catalyzed Reductive Couplings with Imines That Furnish Allylic Amines

“…Our group has investigated the synthesis of both 1,2-diamines (Scheme ) and amino alcohols by reductive couplings of 2-azadienes. , These transformations proceed by means of a copper–hydride intermediate with the bis­(phospholane) Ph-BPE as the ligand. In both cases, the product amines bear an α-alkyl group.…”

Modular synthesis of conjugated enamidines and cascade annulation toward benzofuran-3-oxoacetate

“…Azadienes 2 ( e.g. , 1-aza-1,3-butadienes, 3 2-aza-1,3-butadienes 4 and 1,3-diazabuta-1,3-dienes 5 ) have been proven versatile building blocks in organic synthesis (Scheme 1). Imine 2-aza-1,3-dienes are polyvalent key intermediates for the synthesis of nitrogen compounds and have been widely employed in cycloadditions to access novel and complex heterocyclic derivatives.…”

KOBut/DMSO-Mediated α-C–H Vinylation of N-Benzyl Ketimines with Acetylene Gas: Stereoselective Synthesis of (E,Z)-2-Azadienes

“…The methodology meets pot-, atom-, step-economy (PASE) paradigm requirements. Apart from a contribution to fundamental organic chemistry, this reaction offers a convenient and operationally simple stereoselective synthesis of 2-azadienes, important building blocks for creating molecular complexity and diversity of medicinal and biological importance …”