Development of a Nickel-Catalyzed N–N Coupling for the Synthesis of Hydrazides

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(28), P. 15071 - 15077

Published: July 6, 2023

A nickel-catalyzed N-N cross-coupling for the synthesis of hydrazides is reported. O-Benzoylated hydroxamates were efficiently coupled with a broad range aryl and aliphatic amines via nickel catalysis to form in an up 81% yield. Experimental evidence implicates intermediacy electrophilic Ni-stabilized acyl nitrenoids formation Ni(I) catalyst silane-mediated reduction. This report constitutes first example intermolecular coupling compatible secondary amines.

Language: Английский

---

NiH-Catalyzed Hydroamination/Cyclization Cascade: Rapid Access to Quinolines

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(13), P. 7772 - 7779

Published: June 13, 2021

Despite the significant success of metal-H-catalyzed hydroamination methodologies, considerable limitations still exist in selective alkynes, especially for terminal alkynes. Herein, we develop a highly efficient NiH catalytic system that activates readily available alkynes cascade hydroamination/cyclization reaction with anthranils. This mild, operationally simple protocol is amenable to wide array including and internal, aryl alkyl, electron-deficient electron-rich ones, delivering structurally diverse quinolines useful excellent yields (>80 examples, up 93% yield). The utility this procedure exhibited late-stage functionalization several natural products concise synthesis an antitumor molecule graveolinine triplex DNA intercalator. Preliminary mechanistic experiments suggest alkenylnickel-mediated alkyne intramolecular cyclization/aromatization putative enamine intermediates.

Language: Английский

---

Directed nickel-catalyzed regio- and diastereoselective arylamination of unactivated alkenes

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: Nov. 1, 2021

Few methods have been reported for intermolecular arylamination of alkenes, which could provide direct access to important arylethylamine scaffolds. Herein, we report an syn-1,2-arylamination unactivated alkenes with arylboronic acids and O-benzoylhydroxylamine electrophiles Ni(II) catalyst. The cleavable bidentate picolinamide directing group facilitates formation stabilized 4-, 5- or 6-membered nickelacycles enables the difunctionalization diverse alkenyl amines high levels regio-, chemo- diastereocontrol. This general practical protocol is compatible broad substrate scope functional tolerance. utility this method further demonstrated by site-selective modification pharmaceutical agents.

Language: Английский

---

Enantioselective synthesis of α-aminoboronates by NiH-catalysed asymmetric hydroamidation of alkenyl boronates

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Sept. 26, 2022

Abstract Chiral α-aminoboronic acids and their derivatives are generally useful as bioactive compounds some have been approved therapeutic agents. Here we report a NiH-catalysed asymmetric hydroamidation process that with simple amino alcohol ligand can easily produce wide range of highly enantioenriched α-aminoboronates from alkenyl boronates dioxazolones under mild conditions. The reaction is proposed to proceed by an enantioselective hydrometallation followed inner-sphere nitrenoid transfer C–N bond forming sequence. synthetic utility this transformation was demonstrated the efficient synthesis current pharmaceutical agent, Vaborbactam.

Language: Английский

---

Access to Enantioenriched 1,n-Diamines via Ni-Catalyzed Hydroamination of Unactivated Alkenes with Weakly Coordinating Groups

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(15), P. 9638 - 9645

Published: July 25, 2022

Enantioenriched 1,2- and 1,3-diamines with chiral α-branched aliphatic amine motifs are important substructures in bioactive compounds related molecules serve as privileged ligands both organo- transition-metal-catalysis. However, direct access to such structural remains a formidable challenge. Herein, straightforward method 1,n-diamines (n = 2, 3, 4) containing is achieved by Ni-catalyzed asymmetric hydroamination of unactivated alkenes. Facilitated remote weakly coordinating group, the reaction applicable terminal internal alkenes, delivering enantioenriched 1,2-, 1,3-, 1,4-diamine precursors good yields excellent enantioselectivities diverse substitution patterns. Unactivated alkenes secondary alkyl nucleophile surrogates presence Ni–H, forging C–N bond enantioselectively aminating reagents. In addition, proceeds at room temperature functional group tolerance.

Language: Английский

---