Synthesis of Trifluoromethylated γ-Lactams through Radical Cascades of N-Cyano Alkenes with CF3SO2Na DOI

Jianchao Cui,

Ye Tong,

Yi Li

et al.

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(23), P. 16090 - 16098

Published: Nov. 12, 2022

We report herein a facile strategy to synthesize trifluoromethylated γ-lactams through trifluoromethylcarbonylation of N-cyano alkenes using readily available CF3SO2Na as the CF3 radical source. A range trifluoromethyl-containing was obtained in good yields. This transition-metal-free protocol is demonstrated with mild conditions, broad substrate scope, functional group tolerance, convenient reagents, and an easy-to-handle operating system.

Language: Английский

Catalytic desymmetrization reactions to synthesize all-carbon quaternary stereocentres DOI
Pengwei Xu, Feng Zhou, Lei Zhu

et al.

Nature Synthesis, Journal Year: 2023, Volume and Issue: 2(11), P. 1020 - 1036

Published: Oct. 16, 2023

Language: Английский

Citations

44

Nickel-Catalyzed Enantioselective Reductive Arylation and Heteroarylation of Aldimines via an Elementary 1,4-Addition DOI
Luoqiang Zhang, Xiuhua Wang, Maoping Pu

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(15), P. 8498 - 8509

Published: April 6, 2023

Nickel catalysts of chiral pyrox ligands promoted enantioselective reductive arylation and heteroarylation aldimines, using directly (hetero)aryl halides sulfonates. The catalytic can also be conducted with crude aldimines generated from condensation aldehydes azaaryl amines. Mechanistically, density functional theory (DFT) calculations experiments pointed to an elementary step 1,4-addition aryl nickel(I) complexes N-azaaryl aldimines.

Language: Английский

Citations

26

Enable biomass-derived alcohols mediated alkylation and transfer hydrogenation DOI Creative Commons
Xixi Liu, Liang Huang,

Yuandie Ma

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Aug. 15, 2024

A single-atom catalyst with generally regarded inert Zn–N4 motifs derived from ZIF-8 is unexpectedly efficient for the activation of alcohols, enabling alcohol-mediated alkylation and transfer hydrogenation. C-alkylation nitriles, ketones, N-heterocycles, amides, keto acids, esters, N-alkylation amines amides all go smoothly developed method. Taking α-alkylation nitriles alcohols as an example, starts (1) nitrogen-doped carbon support catalyzed dehydrogenation into aldehydes, which further condensed to give vinyl followed by (2) hydrogenation C=C bonds in on sites. The experimental results DFT calculations reveal that Lewis acidic Zn-N4 sites promote step activating alcohols. This first example highly catalysts various organic transformations biomass-derived alkylating reagents hydrogen donors. Using carbonyl compounds or synthesis α-alkylated appealing a sustainability perspective. Here, acting acid effectively activates thus promoting reactions using both

Language: Английский

Citations

15

Enantioselective Construction of Quaternary Stereocenters via Cooperative Photoredox/Fe/Chiral Primary Amine Triple Catalysis DOI
Lianjie Li,

J.Z.H. Zhang,

W. Li

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(13), P. 9404 - 9412

Published: March 20, 2024

The catalytic and enantioselective construction of quaternary (all-carbon substituents) stereocenters poses a formidable challenge in organic synthesis due to the hindrance caused by steric factors. One conceptually viable potentially versatile approach is coupling C–C bond through an outer-sphere mechanism, accompanied realization enantiocontrol cooperative catalysis; however, examples such processes are yet be identified. Herein, we present method for creating different compounds with photoredox/Fe/chiral primary amine triple catalysis. This facilitates connection unactivated alkyl source tertiary moiety, which also rare. scalable process exhibits mild conditions, does not necessitate use base, possesses good functional-group tolerance. Preliminary investigations into underlying mechanisms have provided valuable insights reaction pathway.

Language: Английский

Citations

14

Nickel-Catalyzed Enantioselective Reductive Arylation of Common Ketones DOI
Shuai Huang, Jianrong Steve Zhou

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(19), P. 12895 - 12900

Published: May 2, 2024

A nickel complex of chiral bisoxazolines catalyzed the stereoselective reductive arylation ketones in high enantioselectivity. range common acyclic and cyclic reacted without aid directing groups. Mechanistic studies using isolated a bis(oxazoline) (L)Ni(Ar)Br revealed that Mn reduction was not needed, while Lewis acidic titanium alkoxides were critical to ketone insertion.

Language: Английский

Citations

11

Recent Advances in Nonprecious Metal Catalysis DOI
Michael C. Haibach, Shashank Shekhar, Tonia S. Ahmed

et al.

Organic Process Research & Development, Journal Year: 2023, Volume and Issue: 27(3), P. 423 - 447

Published: Feb. 17, 2023

Nonprecious-metal-catalyzed alternatives to powerful precious metal transformations are of increasing interest in academia and the pharmaceutical industry due lower cost, better sustainability, toxicity. With continual growth broad field nonprecious catalysis (NPMC), we have chosen highlight selected articles published from March June 2022 which intended examples NPMC that feel may be especially relevant development. We aim inspire academic industrial innovation through discussion herein.

Language: Английский

Citations

23

Role of Noncovalent Interactions in Inducing High Enantioselectivity in an Alcohol Reductive Deoxygenation Reaction Involving a Planar Carbocationic Intermediate DOI

Supratim Ghosh,

Avtar Changotra,

David A. Petrone

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(5), P. 2884 - 2900

Published: Jan. 25, 2023

The involvement of planar carbocation intermediates is generally considered undesirable in asymmetric catalysis due to the difficulty gaining facial control and their intrinsic stability issues. Recently, suitably designed chiral catalyst(s) have enabled a guided approach nucleophiles one prochiral faces carbocations affording high enantiocontrol. Herein, we present vital mechanistic insights from our comprehensive density functional theory (B3LYP-D3) study on Ir-phosphoramidite-catalyzed reductive deoxygenation racemic tertiary α-substituted allenylic alcohols. catalytic transformation relies synergistic action phosphoramidite-modified Ir catalyst Bi(OTf)3, first leading formation an Ir-π-allenyl intermediate through turn-over-determining SN1 ionization, followed by face-selective hydride transfer Hantzsch ester analogue yield enantioenriched product. Bi(OTf)3 was found promote significant number ionic interactions as well noncovalent (NCIs) with substrates (allenylic alcohol ester), thus providing access lower energy route compared pathways devoid Bi(OTf)3. In nucleophilic addition, induction depend efficacy such key NCIs. curious case reversal enantioselectivity, when α-substituent allenyl changed methyl cyclopropyl, identified originate change mechanism enantioconvergent pathway (α-methyl) dynamic kinetic (α-cyclopropyl). These molecular could lead newer strategies tame enantioselective reactions using suitable combinations catalysts additives.

Language: Английский

Citations

20

Amino Acid-Derived Ionic Chiral Catalysts Enable Desymmetrizing Cross-Coupling to Remote Acyclic Quaternary Stereocenters DOI Creative Commons
Junqiang Wei, Vincent Gandon, Ye Zhu

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(30), P. 16796 - 16811

Published: July 20, 2023

Synthetic application of asymmetric catalysis relies on strategic alignment bond construction to creation chirality a target molecule. Remote desymmetrization offers distinctive advantages spatial decoupling catalytic transformation and generation stereogenic element. However, such separation presents substantial difficulties for the chiral catalyst discriminate distant enantiotopic sites through reaction three or more bonds away from prochirality center. Here, we report strategy that establishes acyclic quaternary carbon stereocenters cross-coupling reactions at distal positions aryl substituents. The new class amino acid-derived ionic catalysts enables desymmetrizing (enantiotopic-group-selective) Suzuki-Miyaura reaction, Sonogashira Buchwald-Hartwig amination between diverse diarylmethane scaffolds aryl, alkynyl, coupling partners, providing rapid access enantioenriched molecules project substituents widely spaced in three-dimensional space. Experimental computational investigations reveal electrostatic steering substrates by C-terminus ligands interactions. Cooperative ion-dipole interactions catalyst's amide group potassium cation aid preorganization transmits asymmetry product. This study demonstrates it is practical achieve precise long-range stereocontrol engineering arrangements catalysts' substrate-recognizing groups metal centers.

Language: Английский

Citations

19

Enantioselective Reductive Conjugate Alkenylation of α,β-Unsaturated Ketones and Amides via Nickel Catalysis DOI
Mengxin Zhao, Luoqiang Zhang, Jianrong Steve Zhou

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(8), P. 6228 - 6235

Published: April 10, 2024

Chiral nickel complexes promoted enantioselective reductive alkenylation of a range conjugated enones, using alkenyl bromides, triflates, and tosylates. The neutral condition was compatible with sensitive groups azaheteroaryl rings. Importantly, in products can be readily converted to functionalized alkyl via iron-catalyzed hydrofunctionalization. Some examples asymmetric N-enoyl pyrroles indoles were also included.

Language: Английский

Citations

8

P,N Ligand in Ni-Catalyzed Cross-Coupling Reactions: A Promising Tool for π-Functionalization DOI
Jae‐Han Bae, Eun Jin Cho

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(20), P. 13540 - 13560

Published: Oct. 6, 2023

Bidentate P,N ligands, integrating phosphine and nitrogen donors, are highlighted for their versatile characteristics, offering both electronic steric tunability. Their hemilabile nature, coupled with the ability to modulate properties through choice of donor atoms substituents, has expanded horizons chemical transformations. This Review focuses on Ni-catalyzed cross-coupling reactions mediated by ligands. The asymmetrical nature each atom playing a specific role in catalytic cycle, offers control, stability, unique regioselectivity processes. In particular, Ni/P,N-catalytic system exhibits remarkable reactivity π-substrates including alkenes, alkynes, allenes. A thorough mechanistic understanding these processes insights into trends future directions Ni/P,N-catalyzed reactions.

Language: Английский

Citations

15