Enantioselective Copper‐Catalyzed Sequential Hydrosilylation of Arylmethylenecyclopropanes DOI
Bin Fu, Lianghua Wang, Kexin Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: July 18, 2024

Abstract Despite impressive advances in the construction of enantioenriched silacarbocycles featuring silicon‐stereogenic centers via a selection well‐defined sila‐synthons, development more convenient and economic method with readily available starting materials is significantly less explored remains considerable challenge. Herein, we report first example copper‐catalyzed sequential hydrosilylation accessible methylenecyclopropanes (MCPs) primary silanes, affording an efficient route to wide range chiral silacyclopentanes bearing consecutive silicon‐ carbon‐stereogenic excellent enantio‐ diastereoselectivities (generally ≥98 % ee, >25 : 1 dr). Mechanistic studies reveal that these reactions combine intermolecular ring‐opening aryl MCPs intramolecular asymmetric resultant Z / E mixture homoallylic silanes.

Language: Английский

Nickel-Catalyzed Migratory Cross-Coupling Reactions: New Opportunities for Selective C–H Functionalization DOI
You Wang, Yuli He, Shaolin Zhu

et al.

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(23), P. 3475 - 3491

Published: Nov. 16, 2023

ConspectusMigratory cross-coupling via metal migration is a process of significant academic and industrial interest. It provides an attractive alternative for the selective installation functional group at remote C-H positions from simple precursors, thus enabling direct synthesis challenging structures not accessible with traditional cross-coupling. In particular, merger 1,n-Ni/H shift nickel, Ni-catalyzed migratory functionalization precursors has undergone particularly intense development emerged as valuable field research in past few years. This Account will outline recent progress made this arena terms migration-functionalization modes, diverse functionalizations, strategies regio- stereocontrol. Mechanistic studies synthetic applications are also discussed.In detail, we systematically categorize our work into two parts based on modes. first part, platform created sp3 alkenes or alkyl halides iterative 1,2-Ni/H shift-selective The key reactive Ni(II)H species chain-walking could be generated situ either polarity-reversed fashion relying stoichiometric reductants (X-Ni(II)-H) redox-neutral participation nucleophilic coupling partners (FG-Ni(II)-H). One advantage associated NiH system use relatively stable, abundant, safe olefin surrogates instead sensitive organometallics required reactions. Another that including carbonation more amination thiolation smoothly achieved suitable electrophiles their precursors. Finally, to address multifaceted selectivity reactivity issues asymmetric reactions, have developed feasible ligand relay catalytic strategy. dynamic exchange process, one promotes rapid while other highly stereoselective coupling. innovative strategy overcomes formidable challenge stemming difficulty designing single efficiently promote both steps second new sp2 1,4-Ni/H been reported. Starting readily available aryl vinyl partners, situ-generated aryl- vinylnickel(II) undergo reversible along backbone, subsequent various would allow access 1,4-migratory products. success was discovery appropriate A vinyl-to-aryl successfully enables modular ipso/ortho difunctionalization aryl-to-vinyl functionalized trisubstituted alkenes.We hope inspire broad interest future We strongly believe continued efforts fascinating overcome many remaining challenges, cutting-edge ligand/catalyst design enhance selectivity, conceptually modes additional transformations, in-depth mechanistic rational reaction design.

Language: Английский

Citations

32
Metal-free photosensitized radical relay 1,4-carboimination across two distinct olefins DOI Creative Commons
Guangying Tan, Fritz Paulus, Alessia Petti

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(9), P. 2447 - 2454

Published: Jan. 1, 2023

Intermolecular carboamination of olefins offers a powerful platform for the rapid construction structurally complex amines from abundant feedstocks. However, these reactions often require transition-metal catalysis, and are mainly limited to 1,2-carboamination. Herein, we report novel radical relay 1,4-carboimination across two distinct with alkyl carboxylic acid-derived bifunctional oxime esters

Language: Английский

Citations

31
Asymmetric alkyl-alkyl cross-coupling enabled by earth-abundant metal-catalyzed hydroalkylations of olefins DOI Creative Commons
Pengfei Yang, Wei Shu

Chem Catalysis, Journal Year: 2023, Volume and Issue: 3(4), P. 100508 - 100508

Published: Jan. 30, 2023

Language: Английский

Citations

28
Regioselective and Enantioselective Copper‐Catalyzed Hydroaminocarbonylation of Unactivated Alkenes and Alkynes DOI Creative Commons
Yang Yuan, Youcan Zhang, Wenbo Li

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(40)

Published: Aug. 16, 2023

Given the prevalence of amide backbones in marketed pharmaceuticals and their ubiquity as critical binding units natural peptides proteins, it remains important to develop novel methods construct bonds. We report here a general method for anti-Markovnikov hydroaminocarbonylation unactivated alkenes under mild conditions, using copper catalysis combination with hydroxylamine electrophile reagents poly(methylhydrosiloxane) (PMHS) cheap environmentally friendly hydride source. The reaction tolerates variety functional groups efficiently converts terminal alkenes, 1,1-disubstituted cyclic corresponding amides exclusive selectivity (and high enantioselectivities/diastereoselectivities). Additionally, minimal modification alkynes can also undergo tandem hydrogenation-hydroaminocarbonylation alkyl amides.

Language: Английский

Citations

23
Recent advances in C(sp3)–N bond formation via metallaphoto-redox catalysis DOI
Juan Zhang,

Xiao-Die Huan,

Xin Wang

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(50), P. 6340 - 6361

Published: Jan. 1, 2024

In this review, the state-of-the-art advances in radical-involved C(sp 3 )–N bond formation via metallaphotoredox catalysis have been highlighted, which are organized according to different catalytic modes, reaction types, and substrate classes.

Language: Английский

Citations

12
Rhodium‐Catalyzed Asymmetric Hydrogenation and Transfer Hydrogenation of 1,3‐Dipolar Nitrones DOI

Liren Xu,

Tilong Yang, Hao Sun

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(14)

Published: Feb. 17, 2024

Abstract Owing to their distinctive 1,3‐dipolar structure, the catalytic asymmetric hydrogenation of nitrones hydroxylamines has been a formidable and longstanding challenge, characterized by intricate enantiocontrol susceptibility N−O bond cleavage. In this study, transfer were accomplished with tethered TsDPEN‐derived cyclopentadienyl rhodium(III) catalyst (TsDPEN: p ‐toluenesulfonyl‐1,2‐diphenylethylene‐1,2‐diamine), reaction proceeds via novel 7‐membered cyclic transition state, producing chiral up 99 % yield >99 ee. The practical viability methodology was underscored gram‐scale reactions subsequent transformations. Furthermore, mechanistic investigations DFT calculations also conducted elucidate origin enantioselectivity.

Language: Английский

Citations

9
Rhodium(III)-Catalyzed Anti-Markovnikov Hydroamidation of Unactivated Alkenes Using Dioxazolones as Amidating Reagents DOI

Noah Wagner-Carlberg,

Tomislav Rovis

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(49), P. 22426 - 22432

Published: Dec. 1, 2022

The amide is one of the most prevalent functional groups in all pharmaceuticals, and for this reason, reactions that introduce moiety are particular value. Intermolecular hydroamidation alkenes remains an underexplored method synthesis amide-containing compounds. majority procedures exhibit Markovnikov regioselectivity, while current methods anti-Markovnikov somewhat limited to activated alkene substrates or radical processes. Herein, we report a general intermolecular unactivated under mild conditions, utilizing Rh(III) catalysis conjunction with dioxazolone amidating reagents isopropanol as environmentally friendly hydride source. reaction tolerates wide range efficiently converts electron-deficient alkenes, styrenes, 1,1-disubstituted addition their corresponding linear amides. Mechanistic studies reveal reversible rhodium migratory insertion step, leading exquisite selectivity product.

Language: Английский

Citations

37
Enantioselective synthesis of α-aminoboronates by NiH-catalysed asymmetric hydroamidation of alkenyl boronates DOI Creative Commons
Yao Zhang,

Deyong Qiao,

Mei Duan

et al.

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

Citations

36
Intermolecular Redox-Neutral Carboamination of C–C Multiple Bonds Initiated by Transition-Metal-Catalyzed C–H Activation DOI
Zhongyi Zeng, Hui Gao, Zhi Zhou

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(23), P. 14754 - 14772

Published: Nov. 18, 2022

Carboamination of readily available feedstock-like alkenes, alkynes, and allenes has proven to be an efficient powerful tool for the synthesis diverse valuable amine derivatives relevance medicinal chemistry, biochemistry, material science. Among these developed carboamination methodologies, direct use C–H activation strategy leverage process is particularly attractive due ubiquity such bonds in organic molecules. In this review, we provide overview development intermolecular across C–C π-bonds initiated by a redox-neutral nonannulative manner, with emphasis on synthetic mechanistic aspects. principle, review summarized reactions key feature involving initial metalation followed migratory insertion into terminated electrophilic amination quenching, thus, it ordered sources C- N-based functionalities further divided π-compounds.

Language: Английский

Citations

30
Photocatalytic Anti-Markovnikov Hydroamination of Alkenes with Primary Heteroaryl Amines DOI
Eric P. Geunes, Jonathan M. Meinhardt, Emily J. Wu

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(40), P. 21738 - 21744

Published: Oct. 3, 2023

We report a light-driven method for the intermolecular anti-Markovnikov hydroamination of alkenes with primary heteroaryl amines. In this protocol, electron transfer between an amine substrate and excited-state iridium photocatalyst affords aminium radical cation (ARC) intermediate that undergoes C–N bond formation nucleophilic alkene. Integral to reaction success is electronic character amine, wherein increasingly electron-deficient amines generate reactive ARCs. Counteranion-dependent reactivity observed, triflate photocatalysts are employed in place conventional hexafluorophosphate complexes. This exhibits broad functional group tolerance across 55 examples N-alkylated products derived from pharmaceutically relevant

Language: Английский

Citations

22