Metallaphotoredox-Catalyzed Three-Component Asymmetric Cross-Electrophile Coupling for Chiral Boronate Synthesis DOI
Xiaofang Li, Yuntong Hu,

Zhonghou Huang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(20), P. 15790 - 15798

Published: Oct. 10, 2024

Here, we report a photoredox and nickel-catalyzed cross-electrophile coupling strategy for the asymmetric three-component 1,2-alkylarylation of vinyl boronates with (hetero)aryl bromides (2°, 3°)-alkyl redox-active esters in presence Hantzsch ester. With fluorinated pyridyl-substituted chiral biimidazoline ligand, this reaction enables straightforward access to wide variety synthetically valuable α-aryl from readily available starting materials. This features mild conditions, broad substrate generality, good functional group tolerance proceeds without using metal reductants or alkyl halides. Furthermore, alkenyl halides other electron-deficient alkenes such as acrylates phosphonates can be applied successfully. Preliminary mechanistic studies shed light on potential pathways roles organic amines.

Language: Английский

Ligand-enabled, Ni-catalyzed dicarbofunctionalization of alkenyl alcohols DOI

Li‐Qin She,

Daoming Wang, Yichen Wu

et al.

Chem Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 101261 - 101261

Published: Feb. 1, 2025

Language: Английский

Citations

0
Enantioselective Cobalt-Catalyzed Remote Hydroboration of Alkenylboronates DOI
Wenke Dong,

Zheming Liu,

Aoxuan Bai

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 14, 2025

Heteroatomic groups in alkenes typically direct thermodynamically favored chain walking of C═C bonds toward themselves, thereby facilitating C-H bond functionalization near the heteroatoms. We present herein an efficient cobalt-catalyzed contra-thermodynamic remote hydroboration alkenylboronates with pinacolborane to synthesize chiral 1,n-diboronates. This protocol features a broad substrate scope, high functional group tolerance, and excellent enantioselectivity. Mechanistic studies indicate involvement chain-walking process. Gram-scale reactions various product derivatizations further highlight its practicality.

Language: Английский

Citations

0
Palladium-catalyzed enantioselective β-hydride elimination for the construction of remote stereocenters DOI Creative Commons
Shaozi Sun, Shengnan Sun, Weiwei Zi

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: March 5, 2025

The β-H elimination is a crucial elementary step in transition-metal catalysis, but controlling the stereochemistry of this process has been underdeveloped. limited works reported so far have only focused on creating axial chirality allenes, and no report able to build central using asymmetric elimination. In study, we Trost ligand-enabled enantioselective desymmetric reaction from π-allyl-Pd. This transformation provides rapid access cyclohexenes bearing C4-remoted stereocenter, total synthesis (-)-oleuropeic acid (-)-7-hydroxyterpineol demonstrated. Computational studies shown that rate-determining step, non-covalent interactions between amide moiety ligand benzene cyclohexane moieties substrate play key role stereocontrol during

Language: Английский

Citations

0
Cobalt-Catalyzed Remote Site-Selective Hydroboration of Unactivated Alkenes via Chain-Walking Strategy DOI
Zhiqiang Wang,

Mengjie Zhang,

Xue Li

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

An expedient synthesis of α-aminoboronic acid derivatives via cobalt-catalyzed remote site-selective hydroboration unactivated alkenes is described herein. The strategy characterized by its simplicity, site-selectivity, and wide substrate scope, as both terminal internal could undergo the reaction smoothly, affording corresponding products in good yields. According to mechanism, Co-H generated from Co(acac)2 presence HBpin, which starts chain-walking a series alkene insertion β-H elimination process.

Language: Английский

Citations

0
MeOH-Triggered Halogen-Atom Transfer of Unactivated Alkyl Bromides Enabling the Photoredox Giese Addition DOI

Xian‐Chen He,

Yanling Liu, Jie Gao

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 18, 2025

Herein, a nickel-catalyzed, photoredox Giese addition reaction with readily accessible alkyl bromides, driven by available feedstock MeOH as the halogen-atom transfer (XAT) reagent, was successfully achieved under mild conditions. The versatility of this protocol demonstrated through range structurally varied bromides and Giese-type acceptors moderate to good yields. Mechanistic investigation highlights that formation radicals XAT tentatively prompted •CH2OH, which derived from sequential photo-oxidation/1,2-hydrogen-atom MeOH.

Language: Английский

Citations

0
Approach Toward Stereoselective α‐Arylation by Pd/Cu‐Catalyzed Arylboration of Electron Deficient Alkenes DOI Creative Commons
Suman Das,

Michael Reilly,

Stanna K. Dorn

et al.

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: March 27, 2025

Abstract Palladium‐catalyzed cross coupling of enolates—α‐arylation—is an established method for chemical synthesis. A major challenge in the field is control stereochemistry α‐carbon. This typically due to facile epimerization under basic reaction conditions α‐arylation. In this study, alternative approach presented that involves Pd/Cu‐catalyzed arylboration electron deficient alkenes. The products are generated with high levels diastereoselectivity a broad range substitution patterns. Enantioselective variants also addition product derivatizations.

Language: Английский

Citations

0
Approach Toward Stereoselective α‐Arylation by Pd/Cu‐Catalyzed Arylboration of Electron Deficient Alkenes DOI Creative Commons
Suman Das,

Michael Reilly,

Stanna K. Dorn

et al.

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: March 27, 2025

Abstract Palladium‐catalyzed cross coupling of enolates—α‐arylation—is an established method for chemical synthesis. A major challenge in the field is control stereochemistry α‐carbon. This typically due to facile epimerization under basic reaction conditions α‐arylation. In this study, alternative approach presented that involves Pd/Cu‐catalyzed arylboration electron deficient alkenes. The products are generated with high levels diastereoselectivity a broad range substitution patterns. Enantioselective variants also addition product derivatizations.

Language: Английский

Citations

0
Nickel-Catalyzed 1,1-Carboboration of Polysubstituted Internal Alkenes DOI
Yao Tong, Shiyang Wang, Yu Liu

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

Herein, we report a nickel-catalyzed 1,1-carboboration of di- and trisubstituted alkenyl boronates through chain-walking strategy. This reaction effectively addresses the polarity-mismatch problem via ligand control, enabling coupling various carbon-based electrophiles while accommodating broad range functional groups. The approach yields diverse tetrasubstituted carbon gem-diboronate derivatives with exceptional regioselectivity. synthetic utility this method is further demonstrated concise synthesis high-value bioactive molecules.

Language: Английский

Citations

0
Amide-Directed Rhodium-Catalyzed Chain-Walking Hydrothiolation of Internal Alkenes DOI

Naoki Hikida,

Yasuharu Yoshimi, Hirotsugu Suzuki

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(12), P. 2500 - 2504

Published: March 18, 2024

We developed a rhodium-catalyzed chain-walking hydrothiolation process for internal alkenes, which offers novel and efficient alternative C(sp3)–H bond cleavage, while focusing on thiol incorporation. This method exclusively affords N,S-acetals at 36–90% yields. Regioconvergent significantly improved the effectiveness of this transformation. Preliminary mechanistic investigations revealed that an amide-directing group is essential regioselective synthesis, underlining its significance in process.

Language: Английский

Citations

3
Nickel-Catalyzed Mono- and Dihydrosilylation of Aliphatic Alkynes in Aqueous and Aerobic Conditions DOI

Chanmi Lee,

Ji Hwan Jeon,

Soochan Lee

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 5077 - 5087

Published: March 20, 2024

1,1-Disilanes are synthetically versatile building blocks, owing to their low toxicity, high stability, and unique structures. However, the practical synthesis of 1,1-disilanes is still a challenge. Despite available Fe-, Co-, La-, B-catalyzed protocols, use highly reactive reductants, such as EtMgBr, NaBHEt3, or KHMDS, inevitably requires air- moisture-free conditions. Herein, we report homogeneous Ni-catalyzed mono- dihydrosilylation aliphatic terminal alkynes under either air water conditions neat conditions, affording β-(E)-vinylsilanes in yields with complete regioselectivity stereoselectivity. Importantly, our method gram-scalable sole example alkynes. We demonstrated introduction different silyl groups through stepwise addition each silane source reaction vessel. Furthermore, intermediates were characterized spectroscopic/spectrometric tools, density functional theory calculations performed understand mechanism origins for 1,1-disilanes.

Language: Английский

Citations

3