Stereodivergent Zweifel Olefination and its Mechanistic Dichotomy DOI
Samir Manna,

Swagata Paul,

Wang‐Yeuk Kong

и другие.

Angewandte Chemie, Год журнала: 2023, Номер 135(38)

Опубликована: Июль 27, 2023

Abstract Stereoselective Zweifel olefination using boronate complexes carrying two different reactive π ‐ systems was achieved to synthesize vinyl heteroarenes and conjugated 1,3‐dienes in good yield up 100 % stereoselectivity, which remains unexplored until now. Most importantly, we report the unprecedented formation of E vs. Z ‐vinyl for under identical conditions. Density functional theory (DFT) investigations unveil mechanistic dichotomy between olefin heteroarene activation followed by 1,2‐migration, leading or respectively. We also a previously unknown reversal stereoselectivity 2,3‐Dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) as an electrophile. The complex that carries olefins due significant challenges associated with site‐selective olefins. have solved this problem reported stereoselective synthesis 1,3‐dienes.

Язык: Английский

Anti-Markovnikov hydroallylation reaction of alkenes via scandium-catalyzed allylic C‒H activation DOI Creative Commons

Shiyu Wang,

Lichao Ning,

Tao Mao

и другие.

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Фев. 6, 2025

Compared with rare-earth (RE)…heteroatom interaction, RE…π frequently used in facilitating regio- and stereoselectivity of olefin polymerizations, is seldomly to trigger catalytic C - H functionalization. Here, we describe a direct anti-Markovnikov hydroallylation reaction styrene derivatives 1-aryl-2-alkyl alkenes α-alkenes by use interaction. This protocol provides straightforward atom-efficient route for the synthesis valuable chain elongated internal (65 examples, up 99% yield, > 19:1 E/Z ratio). The proceeds via an allylic Csp3‒H activation pathway initiated site-selective deprotonation assistance cationic imidazolin-2-iminato scandium alkyl species followed alkene insertion into resulting scandium-allyl bond. A amount Lewis base additives, such as amine tetrahydrofuran (THF) show significant effects on reactivity selectivity. mechanism elucidated experimental studies theoretical calculations.

Язык: Английский

Процитировано

4
1,3-diene-based AIEgens: Stereoselective synthesis and applications DOI Creative Commons

Xiao‐Mei Nong,

Ao Gu,

Shuyang Zhai

и другие.

iScience, Год журнала: 2024, Номер 27(3), С. 109223 - 109223

Опубликована: Фев. 15, 2024

SummaryIn recent years, significant advancements have been made in the synthesis and application of 1,3-dienes. This specific structural motif has garnered attention from researchers materials science biology due to its unique aggregation-induced emission (AIE) properties extensive conjugation systems. The luminescent characteristics these compounds are notably influenced by geometry two double bonds. Therefore, it is essential consolidate stereoselective synthetic strategies for comprehensive review seeks elucidate diverse techniques employed attain stereo-control 1,3-diene-based AIE luminogens (AIEgens). Particular emphasis placed on comprehending determinants stereoselectivity exploring array substrates amenable methods. Furthermore, underscores exhibited their utility organic light-emitting diodes (OLEDs), stimuli-responsive materials, sensors, bioimaging, photodynamic therapy (PDT).Graphical abstract

Язык: Английский

Процитировано

7
Stereodivergent Zweifel Olefination and its Mechanistic Dichotomy DOI
Samir Manna,

Swagata Paul,

Wang‐Yeuk Kong

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(38)

Опубликована: Июль 27, 2023

Stereoselective Zweifel olefination using boronate complexes carrying two different reactive π-systems was achieved to synthesize vinyl heteroarenes and conjugated 1,3-dienes in good yield up 100 % stereoselectivity, which remains unexplored until now. Most importantly, we report the unprecedented formation of E vs. Z-vinyl for under identical conditions. Density functional theory (DFT) investigations unveil mechanistic dichotomy between olefin heteroarene activation followed by 1,2-migration, leading or respectively. We also a previously unknown reversal stereoselectivity 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) as an electrophile. The complex that carries olefins due significant challenges associated with site-selective olefins. have solved this problem reported stereoselective synthesis 1,3-dienes.

Язык: Английский

Процитировано

9
N2 Dissociation vs Reversible 1,2-Methyl Migration in PCNHCP Cobalt(I) Complexes in the Stereoselective Isomerization (E/Z) of Allyl Ethers DOI Creative Commons
Sakthi Raje, Subhash Garhwal, Katarzyna Młodzikowska‐Pieńko

и другие.

JACS Au, Год журнала: 2024, Номер 4(11), С. 4234 - 4248

Опубликована: Сен. 18, 2024

With growing efforts pushing toward sustainable catalysis, using earth-abundant metals has become increasingly important. Here, we present the first examples of cobalt PC

Язык: Английский

Процитировано

3
Chromium-Catalyzed Alkene Isomerization with Switchable Selectivity DOI

Jiaoyue Zhong,

Xuelan Wang,

Meiming Luo

и другие.

Organic Letters, Год журнала: 2024, Номер 26(15), С. 3124 - 3129

Опубликована: Апрель 9, 2024

We report a single additive-responsive chromium-catalyzed system for selectively producing either of two different internal alkene isomers. The chromium catalyst, in the presence HBpin/LiOtBu, enables isomerization alkenes over multiple carbon atoms to give most thermodynamically stable same catalyst allows selective terminal one atom without an additive, exhibiting efficient and controllable transposition selectivity.

Язык: Английский

Процитировано

2
Ligand-Controlled Cobalt-Catalyzed Regiodivergent and Stereoselective Ring-Opening Isomerization of Vinyl Cyclopropanes DOI

Wei Wang,

Qiao Li,

Man Xu

и другие.

Organic Letters, Год журнала: 2024, Номер 26(23), С. 5004 - 5009

Опубликована: Июнь 3, 2024

A ligand-controlled regiodivergent and stereoselective ring-opening isomerization of vinylcyclopropane was developed with cobalt catalysis. Employing the commercially available Xantphos ligand, reactions afforded exclusively linear-type 1,3-dienes as products. Interestingly, when switching ligand to an amido-diphosphine (PNP), branched-type were obtained high regioselectivity stereoselectivity. Preliminary mechanistic investigations suggested that a π-allyl metal metal-hydride species are involved key intermediates in two transformations, respectively.

Язык: Английский

Процитировано

1
Cobalt-Catalyzed Borylative Reduction of Azobenzenes to Hydrazobenzenes via a Diborylated-Hydrazine Intermediate DOI

Wenli Wang,

Yuli Wang, Yiying Yang

и другие.

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(13), С. 9265 - 9274

Опубликована: Июнь 20, 2024

Cobalt-catalyzed borylative reduction of azobenzenes using pinacolborane is developed. The simple cobalt chloride catalyst and reaction conditions make this protocol attractive for hydrazobenzene synthesis. This shows good functional group compatibility can be readily scaled up to the gram scale. Preliminary mechanistic studies clarified proton source hydrazine products. cobalt-catalyzed azobenzene provides a practical prepare synthetically useful diborylated hydrazines.

Язык: Английский

Процитировано

1
Cobalt-Catalyzed Synthesis of Alkenyl Heterocycles via Regioselective Intramolecular 1,4-Hydrofunctionalization of Dienes DOI
Chi‐Fan Zhu, Yuan Tian,

Jun-Ju Mai

и другие.

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Сен. 25, 2024

We report a novel cobalt-catalyzed intramolecular 1,4-hydrofunctionalization of dienes. The reaction proceeds under mild conditions and is amenable to N- O-nucleophiles. protocol exhibits exclusive regioselectivity, yielding number different alkenyl heterocycles, including but not limited dihydroisobenzofurans, isochromanes, tetrahydrofurans, morpholines, lactones, isoindolines. Experimental studies were performed offer some insight into the mechanistic pathways rationalize regio- stereoselectivities reaction.

Язык: Английский

Процитировано

1
Insights into the ruthenium-catalysed selective reduction of cardanol derivatives via transfer hydrogenation: a density functional theory study DOI Creative Commons
Shahbaz Ahmad, L. Ellis Crawford, Muhammad Bılal

и другие.

Catalysis Science & Technology, Год журнала: 2023, Номер 13(9), С. 2662 - 2674

Опубликована: Янв. 1, 2023

The detailed mechanism for ruthenium-catalysed selective reduction of cardanol derivatives by transfer hydrogenation has been fully characterised at the B3PW91-D3/ECP2/PCM//B3PW91/ECP1 level density functional theory.

Язык: Английский

Процитировано

3
Reversible 1,2-Methyl Migration to an N-Heterocyclic Carbene in a PCNHCP Cobalt(I) Complex Enables Stereoselective (E and Z) Allyl Ether Isomerization DOI Creative Commons
Subhash Garhwal, Sakthi Raje, Katarzyna Młodzikowska‐Pieńko

и другие.

Опубликована: Ноя. 16, 2023

With growing efforts pushing towards sustainable catalysis, using earth-abundant metals has become increasingly important. Here we present the first examples of cobalt PCNHCP pincer complexes that demonstrate dual stereoselectivity for allyl ether isomerization. While cationic complex [((PCNHCP)Co)2-μ-N2][BAr4F]2 (3) affords Z-isomer enol predominantly, corresponding methyl [(PCNHCP)CoMe)] (4) mostly gives E-isomer. The dichotomy in selectivity is investigated computationally, revealing important contributions from steric profile substituents on metal (Me or N2), including an unprecedented migration substituent to N-heterocyclic carbene carbon, which further explored this report.

Язык: Английский

Процитировано

2