Catalytic Arylalkylation of Alkenyl Amines at Remote Sites via Directed Nickel Catalysis DOI
Jian Han,

Yinheng Tang,

Jie Huang

и другие.

Chinese Journal of Chemistry, Год журнала: 2022, Номер 41(6), С. 631 - 636

Опубликована: Ноя. 11, 2022

Comprehensive Summary Directing group‐assisted, transition metal‐catalyzed three‐component difunctionalization of alkenes has emerged as a powerful tool to drive molecular complexity. However, this strategy generally works with the substrates bearing directing groups in close proximity alkene moieties, due preference for formation kinetically stable five‐membered metallacycles. Herein, we have disclosed complementary accomplish nickel‐catalyzed remote arylalkylation alkenyl amines excellent regioselectivity and diastereofidelity, involving rare six‐ or seven‐membered This general protocol is compatible series δ ‐ ε ‐alkenyl amines, providing corresponding valuable , ζ ‐difunctionalized aliphatic that would be difficult synthesize. The coordination bidentate picolinamide auxiliary facile oxidative addition alkyl halides Ni(I) species are key success developed olefin dicarbofunctionalization.

Язык: Английский

A general alkene aminoarylation enabled by N-centred radical reactivity of sulfinamides DOI
Efrey A. Noten, Cody Ng, Robert M. Wolesensky

и другие.

Nature Chemistry, Год журнала: 2024, Номер 16(4), С. 599 - 606

Опубликована: Янв. 16, 2024

Язык: Английский

Процитировано

35
O-Allylhydroxyamine: A Bifunctional Olefin for Construction of Axially and Centrally Chiral Amino Alcohols via Asymmetric Carboamidation DOI

Ruijie Mi,

Zhiying Ding,

Songjie Yu

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(14), С. 8150 - 8162

Опубликована: Апрель 4, 2023

Difunctionalization of olefins offers an attractive approach to access complex chiral structures. Reported herein is the design N-protected O-allylhydroxyamines as bifunctional that undergo catalytic asymmetric 1,2-carboamidation with three classes (hetero)arenes afford amino alcohols via C-H activation. The C═C bond in O-allylhydroxyamine activated by intramolecular electrophilic amidating moiety well a migrating directing group. carboamidation reaction pattern depends on nature (hetero)arene reagent. Simple achiral reacted give centrally β-amino excellent enantioselectivity. employment axially prochiral or racemic heteroarenes afforded both axial and central chirality enantio- diastereoselectivity. In case heteroarenes, coupling follows kinetic resolution s-factor up >600. A nitrene-based mechanism has been suggested based experimental studies, unique mode induction diastereoselectivity proposed. Applications alcohol products have demonstrated.

Язык: Английский

Процитировано

37
Regiospecific Alkene Aminofunctionalization via an Electrogenerated Dielectrophile DOI
Dylan E. Holst, Céline Dorval,

Casey K. Winter

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(15), С. 8299 - 8307

Опубликована: Апрель 6, 2023

Modular strategies to rapidly increase molecular complexity have proven immensely synthetically valuable. In principle, transformation of an alkene into a dielectrophile presents opportunity deliver two unique nucleophiles across alkene. Unfortunately, the selectivity profiles known dielectrophiles largely precluded this deceptively simple synthetic approach. Herein, we demonstrate that dicationic adducts generated through electrolysis alkenes and thianthrene possess profile relative more conventional dielectrophiles. Specifically, these species undergo single perfectly regioselective substitution reaction with phthalimide salts. This observation unlocks appealing new platform for aminofunctionalization reactions. As illustrative example, implement reactivity paradigm address longstanding challenge: diamination distinct nitrogen nucleophiles. Studies mechanism process reveal key alkenyl thianthrenium salt intermediate controls exquisite regioselectivity highlight importance proton sources in controlling sulfonium electrophiles.

Язык: Английский

Процитировано

34
Ni- and Pd-Catalyzed Enantioselective 1,2-Dicarbofunctionalization of Alkenes DOI
Taeho Kang,

Omar Apolinar,

Keary M. Engle

и другие.

Synthesis, Год журнала: 2023, Номер 56(01), С. 1 - 15

Опубликована: Июнь 12, 2023

Abstract Catalytic enantioselective 1,2-dicarbofunctionalization (1,2-DCF) of alkenes is a powerful transformation growing importance in organic synthesis for constructing chiral building blocks, bioactive molecules, and agrochemicals. Both two- three-component context, this family reactions generates densely functionalized, structurally complex products single step. Across several distinct mechanistic pathways at play these transformations with nickel or palladium catalysts, stereocontrol can be obtained through tailored ligands. In Review we discuss the various strategies, mechanisms, catalysts that have been applied to achieve enantioinduction alkene 1,2-DCF. 1 Introduction 2 Two-Component Enantioselective 1,2-DCF via Migratory Insertion 3 Radical Capture 4 Three-Component 5 6 Miscellaneous Mechanisms 7 Conclusion

Язык: Английский

Процитировано

24
Electrophilic Sulfur Reagent Design Enables Directed syn-Carbosulfenylation of Unactivated Alkenes DOI

Zi‐Qi Li,

Yilin Cao, Taeho Kang

и другие.

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(16), С. 7189 - 7197

Опубликована: Апрель 18, 2022

A multi-component approach to structurally complex organosulfur products is described via the nickel-catalyzed 1,2-carbosulfenylation of unactivated alkenes with organoboron nucleophiles and tailored electrophiles. The key development this transformation identification a modular N-alkyl-N-(arylsulfenyl)arenesulfonamide family sulfur Tuning electronic steric properties leaving group in these reagents controls pathway selectivity, favoring three-component coupling suppressing side reactions, as examined computational studies. unique syn-stereoselectivity differs from traditional electrophilic sulfenyl transfer processes involving thiiranium ion intermediate arises directed arylnickel(I) migratory insertion mechanism, elucidated through reaction kinetics control experiments. Reactivity regioselectivity are facilitated by collection monodentate, weakly coordinating native directing groups, including sulfonamides, alcohols, amines, amides, azaheterocycles.

Язык: Английский

Процитировано

32
Nickel‐Catalyzed Enantioselective Reductive Alkyl‐Carbamoylation of Internal Alkenes DOI Creative Commons
Xianqing Wu, Aneta Turlik,

Baixue Luan

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(36)

Опубликована: Июль 12, 2022

Herein, we leverage the Ni-catalyzed enantioselective reductive dicarbofunctionalization of internal alkenes with alkyl iodides to enable synthesis chiral pyrrolidinones bearing vicinal stereogenic centers. The application newly developed

Язык: Английский

Процитировано

30
Intermolecular Redox-Neutral Carboamination of C–C Multiple Bonds Initiated by Transition-Metal-Catalyzed C–H Activation DOI
Zhongyi Zeng, Hui Gao, Zhi Zhou

и другие.

ACS Catalysis, Год журнала: 2022, Номер 12(23), С. 14754 - 14772

Опубликована: Ноя. 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.

Язык: Английский

Процитировано

30
Synthesis of Unprotected β‐Arylethylamines by Iron(II)‐Catalyzed 1,2‐Aminoarylation of Alkenes in Hexafluoroisopropanol DOI Creative Commons
Valentyn Pozhydaiev, Marie Vayer, Claire Fave

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(9)

Опубликована: Дек. 21, 2022

β-Arylethylamines are prevalent structural motifs in molecules exhibiting biological activity. Here we report a sequential one-pot protocol for the 1,2-aminoarylation of alkenes with hydroxylammonium triflate salts and (hetero)arenes. Unlike existing methods, this reaction provides direct entry to unprotected β-arylethylamines remarkable functional group tolerance, allowing key drug-oriented groups be installed two-step process. The use hexafluoroisopropanol as solvent combination an iron(II) catalyst proved essential reaching high-value nitrogen-containing molecules.

Язык: Английский

Процитировано

26
Enantioselective Amino- and Oxycyanation of Alkenes via Organic Photoredox and Copper Catalysis DOI

Siran Qian,

Tanya M. Lazarus,

David A. Nicewicz

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(33), С. 18247 - 18252

Опубликована: Авг. 14, 2023

The β-amino nitrile moiety and its derivatives frequently appear in natural product synthesis, drug design, as ligands asymmetric catalysis. Herein, we describe a direct route to these complex motifs through the amino- oxycyanation of olefins utilizing an acridinium photooxidant conjunction with copper transformation can be rendered by using serine-derived bisoxazoline ligand. Mechanistic studies implicate olefin-first oxidation. scope amines for aminocyanation reaction has been greatly expanded undergoing cation radical intermediate opposed previous N-centered radical-initiated aminocyanations. Furthermore, alkyl carboxylic acids were included nucleophiles this type first time without any decarboxylative side reactions.

Язык: Английский

Процитировано

14
Catalytic Synthesis of β‐(Hetero)arylethylamines: Modern Strategies and Advances DOI Creative Commons
Valentyn Pozhydaiev, Cyprien Muller, Joseph Moran

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(41)

Опубликована: Авг. 21, 2023

Abstract β‐(Hetero)arylethylamines appear in a myriad of pharmaceuticals due to their broad spectrum biological properties, making them prime candidates for drug discovery. Conventional methods preparation often require engineered substrates that limit the flexibility synthetic routes and diversity compounds can be accessed. Consequently, provide rapid versatile access those scaffolds remain limited. To overcome these challenges, chemists have designed innovative modular strategies β‐(hetero)arylethylamine motif, paving way more extensive use future pharmaceuticals. This review outlines recent progresses synthesis (hetero)arylethylamines emphasizes how innovations enabled new levels molecular complexity, selectivity, practicality.

Язык: Английский

Процитировано

13