Transition Metal‐Catalyzed Asymmetric Hydroamination of Alkenes (AHA)

Abstract

Dedicated to Dick Schrock on the occasion of his 60 th birthday.Abstract: The hydroamination of unsaturated carboncarbon linkages allows a facile and highly atom-economical access to industrially relevant nitrogen-containing basic and fine chemicals as well as naturally occurring alkaloid skeletons. Significant research efforts have led to the development of efficient catalyst systems for intra-and intermolecular hydroamination reactions. Of particular interest are hydroaminations promoted by chiral catalysts, in which a new chiral center is generated or chiral substrates are kinetically resolved. This review will give an overview on the current state of the art in this rapidly evolving field of catalysis.

Gold-catalyzed intermolecular hydroamination of allenes with sulfonamides

“…Hydroamination of an N–H bond across a C–C unsaturated bond represents one of the most effective and atom-economical methods to prepare amine derivatives [1–5]. In the case of using allenes, this reaction can lead to allylamines, which are invaluable precursors for the synthesis of natural products and other potentially biologically relevant substances [6].…”

CuH‐Catalyzed Asymmetric Hydroamidation of Vinylarenes

“…This transformation allows direct access to complex amides from simple achiral precursors,a nd is typically catalyzed by Brønsted acids or transition metals. [4] However,f ew enantioselective intermolecular variants have been reported (Scheme 1B). [5] In one example,anasymmetric coupling of cyclic urea derivatives with unactivated terminal olefins using ac hiral gold complex was developed by Widenhoefer.…”

Gold(I)‐Catalyzed Stereoconvergent, Intermolecular Enantioselective Hydroamination of Allenes

“…[1] Within this family of transformations, the intermolecular enantioselective hydroamination (EHA) of allenes is of interest as a potentially expedient route to enantiomerically enriched a-chiral allylic amines, which are important chiral building blocks that are utilized in the synthesis of complex nitrogen-containing molecules. [1] Within this family of transformations, the intermolecular enantioselective hydroamination (EHA) of allenes is of interest as a potentially expedient route to enantiomerically enriched a-chiral allylic amines, which are important chiral building blocks that are utilized in the synthesis of complex nitrogen-containing molecules.…”

“…The intermolecular, enantioselective addition of the N À H bond of an amine or carboxamide derivative across a C À C multiple bond (hydroamination) represents an attractive, atom-economical approach to the synthesis of chiral, nonracemic amines and amine derivatives. [1] Within this family of transformations, the intermolecular enantioselective hydroamination (EHA) of allenes is of interest as a potentially expedient route to enantiomerically enriched a-chiral allylic amines, which are important chiral building blocks that are utilized in the synthesis of complex nitrogen-containing molecules. [2] However, despite considerable efforts in this area, [1] effective intermolecular EHA processes are scarce, [3] and the intermolecular EHA of allenes remains unknown.…”

“…[1] Within this family of transformations, the intermolecular enantioselective hydroamination (EHA) of allenes is of interest as a potentially expedient route to enantiomerically enriched a-chiral allylic amines, which are important chiral building blocks that are utilized in the synthesis of complex nitrogen-containing molecules. [2] However, despite considerable efforts in this area, [1] effective intermolecular EHA processes are scarce, [3] and the intermolecular EHA of allenes remains unknown. [4] One of the challenges associated with the intermolecular EHA of allenes is the regioselectivity of extant hydroamination catalysts, which form predominantly achiral products from electronically unbiased monosubstituted allenes.…”