Jumping in the Chiral Pool: Asymmetric Hydroaminations with Early Metals

Notz, Sebastian; Scharf, Sebastian; Lang, Heinrich

doi:10.3390/molecules28062702

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Molecules

2023

DOI: 10.3390/molecules28062702

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Jumping in the Chiral Pool: Asymmetric Hydroaminations with Early Metals

Sebastian Notz

Sebastian Scharf

Heinrich Lang

Abstract: The application of early-metal-based catalysts featuring natural chiral pool motifs, such as amino acids, terpenes and alkaloids, in hydroamination reactions is discussed and compared to those beyond the chiral pool. In particular, alkaline (Li), alkaline earth (Mg, Ca), rare earth (Y, La, Nd, Sm, Lu), group IV (Ti, Zr, Hf) metal-, and tantalum-based catalytic systems are described, which in recent years improved considerably and have become more practical in their usability. Additional emphasis is directed to… Show more

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2024

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Cited by 3 publications

References 128 publications

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The Effect of Basic Ligands and Alkenes on the Regioselectivity of C−H Additions of Tertiary Amines to Alkenes

Li,

Wang,

Wang

et al. 2024

Chemistry A European J

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Highly regioselective C‒H alkylation reactions of tertiary anilines and tertiary alkyl amines with simple alkenes have been achieved by the use of imidazolin‐2‐iminato scandium alkyl complexes. This protocol provided an efficient and atom‐economical route to structurally diverse tertiary amine derivatives. The basic ligand, a coordinating THF in the catalyst and the substitution of alkene substrates were found to switch the regioselectivity of the C‒H alkylation reactions of tertiary anilines presumably due to the generation of different types of catalytically active species or the formation of relatively stable intermediates. On the basis of the deuterium labeling experiments and KIE experiments, possible catalytical cycles were provided to understand the reaction mechanism as well as the regioselectivity.

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The Effect of Basic Ligands and Alkenes on the Regioselectivity of C−H Additions of Tertiary Amines to Alkenes

Li,

Wang,

Wang

et al. 2024

Chemistry A European J

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show abstract

A chiral pool-derived calcium catalyst for intramolecular hydroamination with enhanced enantioselectivity

Notz,

Rüffer,

Lang

2024

Inorganic Chemistry Communications

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Enantioselective Zirconium-catalyzed Transformations

Pellissier

2024

COC

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The cheaper and less-toxic metals of Group 4 compared with common metals used in catalysis are increasingly applied in catalysis, resulting in the development of many novel greener transformations. Zirconium is abundant, non-toxic, and exhibits a remarkably diversified chemical reactivity among these metals. Since the first asymmetric zirconium-catalyzed reaction disclosed by Nugent in 1992, a wide variety of chiral zirconium catalysts have been proven to be capable of promoting many types of highly enantioselective transformations, spanning from standard reactions, such as Friedel‒Crafts reactions, cycloadditions, aldol reactions, Mannich reactions, epoxidations, nucleophilic additions to carbonyl compounds and derivatives, cyanations, ring-opening reactions, hydroxylations, hydroformylations, carboaluminations among others, to more modern and complex domino and tandem processes. This review aims to collect the major progress achieved in the field of enantioselective transformations of all types promoted by chiral zirconium catalysts, covering the literature since the beginning of 2003 and illustrating the power of these non-toxic catalysts to provide high enantioselectivity in almost all kinds of asymmetric organic reactions. It is divided into ten parts, focussing consecutively on enantioselective Friedel‒Crafts reactions, cycloadditions, aldol reactions, Mannich reactions, epoxidations, additions of alkylzinc reagents to imines, cyanations, ring-opening reactions, hydroxylations, and domino/ tandem reactions. The diversity of these transformations well reflects that of the products synthesized. For example, chiral indole and pyrrole derivatives were prepared from Friedel‒Crafts reactions; pyranones, pyridones and pyrazolidines from cycloadditions; β-hydroxy α-diazo carbonyl compounds, βhydroxy (thio)esters and β-hydroxy-α-amino acid derivatives from aldol reactions; β-amino (thio)esters from Mannich reactions; functionalized epoxides from epoxidations; amines from additions of alkylzinc reagents to imines; amino nitriles from cyanations; 1,2-diamines and β-vinyloxy alcohols from ring-opening processes; 2- hydroxy 1-indanones from hydroxylations; various amines, 1,3-anti-diol monoesters, β-amino esters, α,βdihydroxy acid derivatives, α-amino ketones, indoles, cyclopentane and aryl α-aminophosphonates from domino/ tandem reactions. Furthermore, the utility of these novel methodologies was demonstrated in the total synthesis of numerous essential bioactive products, such as (+)-prelactone C, (+)-9-deoxygoniopypyrone, (+)- coniine, vancomycin, (+)-fusarisetin A, mycolipenic acid, onchidin, indoxacarb, tachykinin receptor antagonists, cerebroprotecting agent MS-153, and L-erythro-sphingosine. The advances achieved in the last three decades demonstrate that the non-toxicity, abundance, and efficiency of zirconium make its application in catalysis suiting the growing demand for more environmentally benign processes, offering the real opportunity to replace other toxic and expensive metals in the near future.

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Jumping in the Chiral Pool: Asymmetric Hydroaminations with Early Metals

Cited by 3 publications

References 128 publications

The Effect of Basic Ligands and Alkenes on the Regioselectivity of C−H Additions of Tertiary Amines to Alkenes

The Effect of Basic Ligands and Alkenes on the Regioselectivity of C−H Additions of Tertiary Amines to Alkenes

A chiral pool-derived calcium catalyst for intramolecular hydroamination with enhanced enantioselectivity

Enantioselective Zirconium-catalyzed Transformations

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