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DOI: 10.1055/s-0034-1380462
C(sp3)–H versus C(sp3)–C(sp) in Activation of Propargylic Amines under Transition-Metal Catalysis
Publikationsverlauf
Received: 01. Februar 2015
Accepted after revision: 23. Februar 2015
Publikationsdatum:
04. Mai 2015 (online)
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Abstract
Transition-metal-catalyzed C–H and C–C bond activation procedures have attracted significant interest as environmentally friendly processes for organic synthesis. This account summarizes transition-metal-catalyzed transformations of propargylic amines through C(sp3)–H and C(sp3)–C(sp) activation, including hydrogen transfer, deacetylenative homocoupling, fragment exchange, and redox cross-dehydrogenative coupling (CDC). The generation of iminium intermediates is essential for the current transformations based on propargylic amines.
1 Introduction
2 Synthesis of Allenes from Propargylic Amines through Palladium-Catalyzed Hydrogen-Transfer Reactions
2.1 Propargylic Amines as Allenyl Anion Equivalents
2.2 Synthesis of Allenyl Carbinols
2.3 Synthesis of Heterocyclic Allenes
2.4 Mechanistic Study
2.5 One-Pot Synthesis of Allenes from Aryl Halides
3 Substitution Reactions of Propargylic Amines through Copper(I)-Catalyzed C(sp)–C(sp3) Bond Activation
3.1 Substitution Reactions of Propargylic Amines with Secondary Amines
3.2 Substitution Reactions of Propargylic Amines with 1-Alkynes
3.3 Deacetylenative Coupling with Various Propargylic Amines
4 Zinc(II)-Catalyzed Redox Cross-Dehydrogenative Coupling of Propargylic Amines and Terminal Alkynes
5 Conclusion
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