Rhodium(III)-Catalyzed Remote Hydroamidation of Internal Alkenes Via Chain Walking

Wagner-Carlberg, Noah; Rovis, Tomislav

doi:10.1021/acscatal.3c05075

Cited by 10 publications

(1 citation statement)

References 50 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The inherent polarity of transition metal hydride (TMH) selectively renders a selective α-metalation of electron-deficient olefins via metal hydride hydrogen atom transfer (MHAT) or 1,4 addition, − eventually forging functionalization at that position to allow α-C–H, C–C, C–O, or C–N bond formation (Scheme b) . In stark contrast, achieving a regioisomeric β-metal insertion through olefin hydrometalation is exceedingly rare. − Indeed, to the best of our knowledge, there are only two examples of asymmetric β-amination of β-aryl-α,β-unsaturated carbonyl compounds via CuH catalysis using electrophilic aminating reagents. , Buchwald et al employed 1,2-benzisoxazole and revealed that the choice of chiral ligands is critical for the control of regioselectivity .…”

Section: Introductionmentioning

confidence: 99%

Enantioselective Access to β-Amino Carbonyls via Ni-Catalyzed Formal Olefin Hydroamidation

Lyu,

Jung,

Kim

et al. 2024

J. Am. Chem. Soc.

View full text Add to dashboard Cite

We herein describe a Ni-catalyzed formal hydroamidation of readily available α,β-unsaturated carbonyl compounds to afford valuable chiral β-amino acid derivatives (up to >99:1 e.r.) using dioxazolones as a robust amino source. A wide range of alkyl-substituted olefins conjugated to esters, amides, thioesters, and ketones were successfully amidated at the β-position with excellent enantioselectivity for the first time. Combined experimental and computational mechanistic studies supported our working hypothesis that this unconventional β-amidation of unsaturated carbonyl substrates can be attributed to the polar-matched migratory olefin insertion of an (amido)(Cl)NiII intermediate, in situ generated from the dioxazolone precursor.

show abstract

Section: Introductionmentioning

confidence: 99%

Enantioselective Access to β-Amino Carbonyls via Ni-Catalyzed Formal Olefin Hydroamidation

Lyu,

Jung,

Kim

et al. 2024

J. Am. Chem. Soc.

View full text Add to dashboard Cite

show abstract

Chiral Osmium(II)/Salox Species Enabled Enantioselective γ‐C(sp³)−H Amidation: Integrated Experimental and Computational Validation For the Ligand Design and Reaction Development

Chen,

Xu,

Liu

et al. 2024

Angewandte Chemie

View full text Add to dashboard Cite

Herein, multiple types of chiral Os(II) complexes have been designed to address the appealing yet challenging asymmetric C(sp3)‐H functionalization, among which the Os(II)/Salox species is found to be the most efficient for precise stereocontrol in realizing the asymmetric C(sp3)‐H amidation. As exemplified by the enantioenriched pyrrolidinone synthesis, such tailored Os(II)/Salox catalyst efficiently enables an intramolecular site‐/enantioselective C(sp3)‐H amidation in the γ‐position of dioxazolone substrates, in which benzyl, propargyl and allyl groups bearing various substituted forms are well compatible, affording the corresponding chiral γ‐lactam products with good er values (up to 99:1) and diverse functionality (> 35 examples). The unique performance advantage of the developed chiral Os(II)/Salox system in terms of the catalytic energy profile and the chiral induction has been further clarified by integrated experimental and computational studies.

show abstract

Methoxide‐Enabled Zirconium‐Catalyzed Migratory Alkene Hydrosilylation

Luongo,

Lemmerer,

Albers

et al. 2024

Angewandte Chemie

View full text Add to dashboard Cite

A zirconocene dichloride‐catalyzed alkene hydrosilylation is reported that can be applied to non‐activated and conjugated terminal and internal alkenes. It involves a catalytic Zr‐walk process and leads to a selective conversion to the linear product. Lithium methoxide serves as mild catalyst activating agent, which significantly increases the applicability and operational simplicity in comparison to earlier zirconium(II)‐based protocols. Supported by additional experiments and calculations, a mechanism via zirconium(IV) intermediates is proposed. Due to the benign nature and ready‐availability of the zirconium catalyst, the reaction is an attractive alternative to established alkene hydrosilylation methods.

show abstract

Rhodium(III)-Catalyzed Remote Hydroamidation of Internal Alkenes Via Chain Walking

Cited by 10 publications

References 50 publications

Enantioselective Access to β-Amino Carbonyls via Ni-Catalyzed Formal Olefin Hydroamidation

Enantioselective Access to β-Amino Carbonyls via Ni-Catalyzed Formal Olefin Hydroamidation

Chiral Osmium(II)/Salox Species Enabled Enantioselective γ‐C(sp³)−H Amidation: Integrated Experimental and Computational Validation For the Ligand Design and Reaction Development

Methoxide‐Enabled Zirconium‐Catalyzed Migratory Alkene Hydrosilylation

Contact Info

Product

Resources

About

Rhodium(III)-Catalyzed Remote Hydroamidation of Internal Alkenes Via Chain Walking

Cited by 10 publications

References 50 publications

Enantioselective Access to β-Amino Carbonyls via Ni-Catalyzed Formal Olefin Hydroamidation

Enantioselective Access to β-Amino Carbonyls via Ni-Catalyzed Formal Olefin Hydroamidation

Chiral Osmium(II)/Salox Species Enabled Enantioselective γ‐C(sp3)−H Amidation: Integrated Experimental and Computational Validation For the Ligand Design and Reaction Development

Methoxide‐Enabled Zirconium‐Catalyzed Migratory Alkene Hydrosilylation

Contact Info

Product

Resources

About

Chiral Osmium(II)/Salox Species Enabled Enantioselective γ‐C(sp³)−H Amidation: Integrated Experimental and Computational Validation For the Ligand Design and Reaction Development