Enantioselective synthesis of α,α-diarylketones by sequential visible light photoactivation and phosphoric acid catalysis DOI Creative Commons
Hong‐Fu Liu, Long Liang, Zhiqiang Zhu

и другие.

Science Advances, Год журнала: 2023, Номер 9(24)

Опубликована: Июнь 16, 2023

Chiral ketones and their derivatives are useful synthetic intermediates for the synthesis of biologically active natural products medicinally relevant molecules. Nevertheless, general broadly applicable methods enantioenriched acyclic α,α-disubstituted ketones, especially α,α-diarylketones, remain largely underdeveloped, owing to easy racemization. Here, we report a visible light photoactivation phosphoric acid–catalyzed alkyne-carbonyl metathesis/transfer hydrogenation one-pot reaction using arylalkyne, benzoquinone, Hantzsch ester expeditious α,α-diarylketones with excellent yields enantioselectivities. In reaction, three chemical bonds, including C═O, C─C, C─H, formed, providing de novo chiral α,α-diarylketones. Moreover, this protocol provides convenient practical method synthesize or modify complex bioactive molecules, efficient routes florylpicoxamid BRL-15572 analogs. Computational mechanistic studies revealed that C-H/π interactions, π-π interaction, substituents all play crucial roles in stereocontrol reaction.

Язык: Английский

Nickel‐Catalyzed Switchable Site‐Selective Alkene Hydroalkylation by Temperature Regulation** DOI
Jia‐Wang Wang, Deguang Liu, Zhe Chang

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(31)

Опубликована: Май 25, 2022

Regiodivergent alkene functionalization that produces either regioisomer starting from the same raw materials is desirable. Herein, we report a nickel-catalyzed switchable site-selective hydroalkylation. The selection of reaction temperatures leads to protocols provide regiodivergent hydroalkylated products single substrate. This protocol allows convenient synthesis α- and β-branched protected amines, both which are important fields pharmaceutical chemistry biochemistry. In addition, enantioenriched alkylamines can be accessed in catalytic asymmetric variant. Preliminary mechanistic studies indicate formation more stable nickelacycle provides driving force migration. thermodynamic kinetic properties different reduction elimination intermediates responsible for site-selectivity.

Язык: Английский

Процитировано

67
Bifunctional Copper Metal–Organic Framework Catalyst for Late-Stage Functionalization of Alkenes DOI
Lu Dong, Hu Chen, Xiaoli Tan

и другие.

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4198 - 4207

Опубликована: Фев. 24, 2025

Язык: Английский

Процитировано

1
Visible light catalyzed arylsilylation of alkenes to construct silicon-containing 1,1-diaryl moieties DOI
Jia Cao, Liuzhou Gao, Guoqiang Wang

и другие.

Green Chemistry, Год журнала: 2024, Номер 26(8), С. 4785 - 4791

Опубликована: Янв. 1, 2024

We have developed an efficient photocatalyzed arylsilylation of alkenes, utilizing silylboranes and (hetero)aryl nitriles in the presence base photocatalyst.

Язык: Английский

Процитировано

8
Nickel‐Catalyzed Enantioconvergent Carboxylation Enabled by a Chiral 2,2′‐Bipyridine Ligand DOI
Linghua Wang, Tao Li, Saima Perveen

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(51)

Опубликована: Окт. 27, 2022

In contrast to previous approaches chiral α-aryl carboxylic acids that based on reactions using hazardous gases, pressurized setup and mostly noble metal catalysts, in this work, a nickel-catalyzed general, efficient highly enantioselective carboxylation reaction of racemic benzylic (pseudo)halides under mild conditions atmospheric CO2 has been developed. A unique 2,2'-bipyridine ligand named Me-SBpy featuring compact polycyclic skeleton enabled both high reactivity stereoselectivity. The utility method demonstrated by synthesis various (30 examples, up 95 % yield 99 : 1 er), including profen family anti-inflammatory drugs transformations the as key intermediates. Based mechanistic experimental results, plausible catalytic cycle involving Ni-complex/radical equilibrium Lewis acid-assisted activation proposed.

Язык: Английский

Процитировано

28
Ligand-enabled Ni-catalyzed hydroarylation and hydroalkenylation of internal alkenes with organoborons DOI Creative Commons
Daoming Wang,

Li‐Qin She,

Yichen Wu

и другие.

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Ноя. 12, 2022

The transition metal-catalyzed hydrofunctionalization of alkenes offers an efficient solution for the rapid construction complex functional molecules, and significant progress has been made during last decades. However, internal remains a challenge due to low reactivity difficulties controlling regioselectivity. Here, we report hydroarylation hydroalkenylation lacking directing group with aryl alkenyl boronic acids in presence nickel catalyst, featuring broad substrate scope wide tolerance under redox-neutral conditions. key achieving this reaction is identification bulky 1-adamantyl β-diketone ligand, which capable overcoming 1,2-disubstituted alkenes. Preliminary mechanistic studies unveiled that undergoes Ar-Ni(II)-H initiated process, generated by oxidative addition alcoholic solvent Ni(0) species sequential transmetalation. In addition, proves be turnover-limiting step.

Язык: Английский

Процитировано

26
Switchable Direct Oxygenative Arylation of C(sp3)–H Bonds via Electrophotocatalysis DOI
Yan Zhang,

Xiang Sun,

Ji‐Hu Su

и другие.

Organic Letters, Год журнала: 2023, Номер 25(27), С. 5067 - 5072

Опубликована: Июнь 30, 2023

A metal-free electrophotochemical C(sp3)-H arylation was developed under mild conditions. This method enables a switchable synthesis of diaryl alcohols and alkanes from inactive benzylic carbons. More importantly, cheap safe mediator N-chlorosuccinimide (NCS) developed, which employed for the hydrogen atom transfer (HAT) process C–H bond. In addition, this active radical captured identified by electron paramagnetic resonance (EPR).

Язык: Английский

Процитировано

15
Lewis Basic Salt-Promoted Organosilane Coupling Reactions with Aromatic Electrophiles DOI

Tyler W. Reidl,

Jeffrey S. Bandar

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(31), С. 11939 - 11945

Опубликована: Июль 27, 2021

Lewis basic salts promote benzyltrimethylsilane coupling with (hetero)aryl nitriles, sulfones, and chlorides as a new route to 1,1-diarylalkanes. This method combines the substrate modularity selectivity characteristic of cross-coupling practicality base-promoted protocol. In addition, base strategy enables complementary scope existing methods, employs stable easily prepared organosilanes, achieves selective arylation in presence acidic functional groups. The utility this is demonstrated by synthesis pharmaceutical analogues its use multicomponent reactions.

Язык: Английский

Процитировано

28
Rhodium(I) Carbene‐Promoted Enantioselective C−H Functionalization of Simple Unprotected Indoles, Pyrroles and Heteroanalogues: New Mechanistic Insights DOI

Tian‐Yi Wang,

Xiao‐Xuan Chen,

Dong‐Xing Zhu

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(34)

Опубликована: Июнь 17, 2022

A rhodium(I)-diene catalyzed highly enantioselective C(sp2 )-H functionalization of simple unprotected indoles, pyrroles, and their common analogues such as furans, thiophenes, benzofurans with arylvinyldiazoesters has been developed for the first time. This transformation features unusual site-selectivity exclusively at vinyl terminus arylvinylcarbene enables a reliable rapid synthetic protocol to access distinctive class diarylmethine-bearing α,β-unsaturated esters containing one or two heteroarene-attached tertiary carbon stereocenter in high yields excellent enantioselectivities under mild reaction conditions. Mechanistic studies DFT calculations suggest that, compared aniline substrate, more electron-rich indole substrate lowers C-C addition barrier alters rate-determining step reductive elimination, leading different isotope effect.

Язык: Английский

Процитировано

23
Efficient Synthesis of Diaryl Quaternary Centers by Rh(II)/Xantphos Catalyzed Relay C−H Functionalization and Allylic Alkylation DOI

Zhaoliang Ge,

Bin Lu, Huailong Teng

и другие.

Chemistry - A European Journal, Год журнала: 2022, Номер 29(3)

Опубликована: Окт. 14, 2022

A three-component reaction of N, N-disubstituted aniline, α-diazo ester, and an allylic electrophile has been realized by [Rh(II)]2 /Xantphos catalysis, providing a direct access to various aniline derivatives bearing diaryl quaternary centers in good yields. The synthetic utility this protocol was demonstrated facile derivatization the products for preparation biologically relevant molecules structural scaffolds, which offers high potential increasing molecular diversity. Mechanistic studies identified α, α-diarylacetate species as active intermediate, thereby revealing presence C(sp2 )-H functionalization derivatives/allylic alkylation cascade attractive catalytic transformation.

Язык: Английский

Процитировано

21
Conformational Locking Induced Enantioselective Diarylcarbene Insertion into B−H and O−H Bonds Using a Cationic Rh(I)/Diene Catalyst DOI

Weici Xu,

Takeshi Yamakawa,

Meiling Huang

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(45)

Опубликована: Июль 18, 2024

Abstract Transition‐metal‐catalyzed enantioselective transformations of aryl/aryl carbene are inherently challenging due to the difficulty in distinguishing between two arene rings reaction process thus remain largely less explored. The few successful examples reported so far, without exception, have all been catalyzed by Rh(II)‐complexes. Herein, we describe our development a novel cationic Rh(I)/chiral diene catalytic system capable efficient B−H and O−H insertions with diaryl diazomethanes, allowing access broad range gem ‐diarylmethine boranes ethers good yields high enantioselectivities. Notably, previously unattainable asymmetric diarylcarbene insertion into bond was achieved for first time. A remarkable feature this newly designed Rh(I)/diene catalyst bearing ortho ‐amidophenyl substitutents is that it can distinguish through stereochemically selective control π–π stacking interactions. DFT calculations indicate rotation‐restricted conformation complex played an important role highly transformations. This work provides interesting unprecedented stereocontrol mode metal

Язык: Английский

Процитировано

5