Copper-Catalysed Selective Hydroamination Reactions of Alkynes

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Submitted By beibeiao
Words 6397
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PUBLISHED ONLINE: 15 DECEMBER 2014 | DOI: 10.1038/NCHEM.2131

Copper-catalysed selective hydroamination reactions of alkynes
Shi-Liang Shi and Stephen L. Buchwald*
The development of selective reactions that utilize easily available and abundant precursors for the efficient synthesis of amines is a long-standing goal of chemical research. Despite the centrality of amines in a number of important research areas, including medicinal chemistry, total synthesis and materials science, a general, selective and step-efficient synthesis of amines is still needed. Here, we describe a set of mild catalytic conditions utilizing a single copper-based catalyst that enables the direct preparation of three distinct and important amine classes (enamines, α-chiral branched alkylamines and linear alkylamines) from readily available alkyne starting materials with high levels of chemo-, regio- and stereoselectivity. This methodology was applied to the asymmetric synthesis of rivastigmine and the formal synthesis of several other pharmaceutical agents, including duloxetine, atomoxetine, fluoxetine and tolterodine.

C

omplex organic molecules play a crucial role in the study and treatment of disease. The extent to which they can be utilized in these endeavours depends on the efficient and selective chemical methods for their construction1. Amines are widely represented in biologically active natural products and medicines2 (a small selection of which are shown in Fig. 1a). Consequently, the selective assembly of amines from readily available precursors is a prominent objective in chemical research3. There are a number of powerful methods that address this challenge, including metal-catalysed cross-coupling4,5, nucleophilic addition to imines6, C–H nitrogen insertion7 and enzymatic methods8,9. However, the direct production of amines from simple olefins or alkynes represents a highly…...

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