Iron–Nickel Dual-Catalysis: A New Engine for Olefin Functionalization and the Formation of Quaternary Centers

Journal of the American Chemical Society, Год журнала: 2018, Номер 140(36), С. 11317 - 11324

Опубликована: Июль 26, 2018

Alkene hydroarylation forms carbon-carbon bonds between two foundational building blocks of organic chemistry: olefins and aromatic rings. In the absence electronic bias or directing groups, only Friedel-Crafts reaction allows arenes to engage alkenes with Markovnikov selectivity generate quaternary carbons. However, intermediacy carbocations precludes use electron-deficient arenes, including Lewis basic heterocycles. Here we report a highly Markovnikov-selective, dual-catalytic olefin that tolerates heteroarenes any character. Hydrogen atom transfer controls formation branched products arene halogenation specifies attachment points on ring. Mono-, di-, tri-, tetra-substituted yield carbons within nonstrained

Язык: Английский

---

Recent advances in asymmetric borylation by transition metal catalysis

Chemical Society Reviews, Год журнала: 2021, Номер 50(23), С. 13129 - 13188

Опубликована: Янв. 1, 2021

We provide a comprehensive overview of transition metal-catalysed asymmetric borylation processes to construct C–B, C–C, and other C–heteroatom bonds with considerable attention devoted the reaction modes mechanisms involved.

Язык: Английский

---

Recent Advances in Nickel-Catalyzed Three-Component Difunctionalization of Unactivated Alkenes

Synthesis, Год журнала: 2020, Номер 52(09), С. 1346 - 1356

Опубликована: Март 2, 2020

Catalytic, intermolecular difunctionalization of alkenes represents an efficient and diverse protocol for the buildup molecular complexity from abundant materials by forging two chemical bonds in a single operation. Despite important progress this area, transition-metal-catalyzed three-component unactivated remains underdeveloped, mainly because low reactivity, reduced polarization, high tendency toward β-hydride elimination these compounds. In context, nickel-catalyzed, selective, methods that generally proceed via distinct reaction pathways, migratory insertion nickel species into radical addition to alkenes, have been developed. This short review highlights recent advances area. 1 Introduction 2 Nickel-Catalyzed Three-Component Difunctionalization Unactivated­ Alkenes Migratory Insertion Processes 3 Radical 4 Conclusions Perspectives

Язык: Английский

---

Nickel Chain-Walking Catalysis: A Journey to Migratory Carboboration of Alkenes

Accounts of Chemical Research, Год журнала: 2023, Номер 56(22), С. 3246 - 3259

Опубликована: Ноя. 1, 2023

ConspectusChain-walking offers extensive opportunities for innovating synthetic methods that involve constructing chemical bonds at unconventional sites. This approach provides previously inaccessible retrosynthetic disconnections in organic synthesis. Through chain-walking, transition metal-catalyzed alkene difunctionalization reactions can take place a 1,n-addition (n ≠ 2) mode. Unlike classical 1,2-regioselective reactions, there remains scarcity of reports regarding migratory patterns. Moreover, the range olefins utilized these studies is quite limited.About five years ago, our research group embarked on project aimed developing valuable alkenes through chain-walking. Our focus was carboboration utilizing nickel catalysis. The reaction commences with insertion an olefin into Ni-Bpin species. Subsequently, thermodynamically stable alkyl complex generated chain-walking process. then couples carbon-based electrophile, leading to formation alkylboron compound. It worth highlighting success transformations relies significantly utilization bisnitrogen-based ligand and LiOMe as B2pin2 activator. Synthetically, establish robust platform rapid efficient synthesis wide structurally diverse organoboron compounds, which are not facially accessed by conventional methods. incorporation versatile boron introduces wealth possibilities subsequent diversifications, enhancing value resulting products allowing creation broader derivatives applications.This Account comprehensive overview efforts advancements field unactivated using We begin outlining development series 1,1-regioselective terminal alkenes. A significant placed initial integration boronate, only triggers metal species but also exerts control over remote stereochemistry involving substituted methylenecyclohexenes. Continuing exploration, remarkable achieved 1,3-regio- cis-stereoselectivity when dealing cyclic Remarkably, catalysis enables heterocyclic be viable coupling partners within transformations. it grants us ability achieve regioselectivity cyclohexenes unattainable, thus expanding horizons regiochemical reactions. Lastly, we present evolution ligand-modulated regiodivergent allylarenes. By gaining insights underlying mechanisms driving regiodivergence, lay strong foundation tackling challenges related selecting specific sites especially multiple factors. anticipate findings, coupled mechanistic we've gained, will advance realm contribute understanding selectivity this nature. advancement catalyze intricate functional molecules, contributing compounds chemistry.

Язык: Английский

---

Enantioselective Reductive Cross-Couplings of Olefins by Merging Electrochemistry with Nickel Catalysis

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(44), С. 23910 - 23917

Опубликована: Окт. 26, 2023

The merger of electrochemistry and transition metal catalysis has emerged as a powerful tool to join two electrophiles in an enantioselective manner. However, the development electroreductive cross-couplings olefins remains challenge. Inspired by advantages synergistic use with nickel catalysis, we present here Ni-catalyzed cross-coupling acrylates aryl halides alkyl bromides, which affords chiral α-aryl carbonyls good excellent enantioselectivity. Additionally, this catalytic reaction can be applied (hetero)aryl chlorides, is difficult achieve other methods. combination cyclic voltammetry analysis electrode potential studies suggests that NiI species activates oxidative addition bromides single-electron transfer.

Язык: Английский

---

Facile Access to Quaternary Carbon Centers via Ni-Catalyzed Arylation of Alkenes with Organoborons

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 16, 2025

Quaternary carbon centers are widespread structural motifs, thus representing extensive interest in organic synthesis. We describe here an efficient nickel-catalyzed intermolecular, Markovnikov-selective arylation of minimally functionalized alkenes with stable organoborons, affording a broad range cyclic or acyclic quaternary under mild conditions. The utilization the diimine ligand is critical for high reactivity and chemoselectivity. Furthermore, using bulky chiral as Ni catalyst, stereocenters can be readily prepared levels enantiocontrol. Mechanism studies suggest that, before protonation, rare nickel shift from alkyl to aryl might occur.

Язык: Английский

---

New Radical Borylation Pathways for Organoboron Synthesis Enabled by Photoredox Catalysis

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(31), С. 12876 - 12884

Опубликована: Март 31, 2020

Radical borylation using N-heterocyclic carbene (NHC)-BH3 complexes as boryl radical precursors has emerged an important synthetic tool for organoboron assembly. However, the majority of reported methods are limited to reaction modes involving carbo- and/or hydroboration specific alkenes and alkynes. Moreover, generation NHC-boryl radicals relies principally on hydrogen atom abstraction with aid initiators. A distinct method is reported, well pathways enabled by photoredox catalysis. generated via a single-electron oxidation subsequently undergo cross-coupling in-situ-generated anions yield gem-difluoroallylboronates. photoredox-catalyzed arylboration was achieved cyanoarenes arylating components from which elaborated organoborons were accessed. Mechanistic studies verified oxidative formation through single-electron-transfer pathway.

Язык: Английский

---

Palladium(0)‐Catalyzed Directed syn‐1,2‐Carboboration and ‐Silylation: Alkene Scope, Applications in Dearomatization, and Stereocontrol by a Chiral Auxiliary

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(47), С. 17068 - 17073

Опубликована: Сен. 20, 2019

Abstract We report the development of palladium(0)‐catalyzed syn ‐selective 1,2‐carboboration and ‐silylation reactions alkenes containing cleavable directing groups. With B 2 pin or PhMe Si‐Bpin as nucleophiles aryl/alkenyl triflates electrophiles, a broad range mono‐, di‐, tri‐ tetrasubstituted are compatible in these transformations. further describe directed dearomative electron‐rich heteroarenes by employing this approach. Through use removable chiral group, we demonstrate viability achieving stereoinduction Heck‐type alkene 1,2‐difunctionalization. This work introduces new avenues to access highly functionalized boronates silanes with precise regio‐ stereocontrol.

Язык: Английский

---

Catalyst-controlled enantioselective 1,1-arylboration of unactivated olefins

Nature Catalysis, Год журнала: 2020, Номер 3(11), С. 951 - 958

Опубликована: Окт. 19, 2020

Язык: Английский

---

Transition‐Metal‐Catalyzed 1,2‐Carboboration of Alkenes: Strategies, Mechanisms, and Stereocontrol

Israel Journal of Chemistry, Год журнала: 2019, Номер 60(3-4), С. 219 - 229

Опубликована: Сен. 10, 2019

Abstract During the past decade, many research groups have described catalytic methods for 1,2‐carboboration, allowing access to structurally complex organoboronates from alkenes. Various transition metals, especially copper, palladium, and nickel, been widely used in these reactions. This review summarizes advances this field, with a special focus on cycles involved different metal‐catalyzed carboboration reactions, as well regio‐ stereochemical consequences of underlying mechanisms. 1,2‐Carboboration other unsaturated systems, such alkynes allenes, is outside scope review.

Язык: Английский

---