Intermolecular radical carboamination of alkenes

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(6), P. 1790 - 1811

Published: Jan. 1, 2020

Vicinal alkene carboamination is a highly efficient and practical synthetic strategy for the straightforward preparation of diverse valuable amine derivatives starting from simple compounds. During last decade that approach has found continuous research interests various methods have been developed using transition-metal catalysis. Driven by renaissance radical chemistry, intermolecular comprising C-C bond C-N forming step intensively investigated recently culminating in novel strategies improved protocols which complement existing methodologies. Radical can be achieved via three different reaction modes. Such cascades proceed through N-radical addition to an with subsequent formation leading 2,1-carboamination products. Alternatively, installed prior initial C-radical β-amination resulting 1,2-carboamination. The third mode comprises single electron oxidation corresponding cation gets trapped N-nucleophile cascade terminated formation. In this review, conceptual approaches will discussed examples recent literature presented. Further, reader get insights into mechanism transformations.

Language: Английский

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Visible-Light-Driven Reductive Carboarylation of Styrenes with CO₂ and Aryl Halides

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(18), P. 8122 - 8129

Published: April 20, 2020

The first example of visible-light-driven reductive carboarylation styrenes with CO2 and aryl halides in a regioselective manner has been achieved. A broad range iodides bromides were compatible this reaction. Moreover, pyridyl halides, alkyl even chlorides also viable method. These findings may stimulate the exploration novel Meerwein arylation-addition reactions user-friendly as radical sources photocatalytic utilization CO2.

Language: Английский

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Copper-Catalyzed Borylative Difunctionalization of π-Systems

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(19), P. 11578 - 11622

Published: Aug. 25, 2020

Organoboronates represent a cornerstone functional group in modern synthesis owing to their unique reactivity and divergent synthetic capability. Copper catalysis has become one of the most powerful methods stereoselectively install boron across diverse π-systems. Additionally, this method affords tremendous versatility enabled by difunctionalization π-system addition an electrophile. This review covers known electrophiles intercept catalytic intermediates borylative strategies that have been reported up end May 2020.

Language: Английский

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Recent developments in the difunctionalization of alkenes with C–N bond formation

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(18), P. 5206 - 5228

Published: Jan. 1, 2021

Various alkene difunctionalization reactions involving nitridization, diamination, azidation, oxyamination, carboamination, aminohalogenation, and nitration are introduced in this review.

Language: Английский

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

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(22), P. 3246 - 3259

Published: Nov. 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.

Language: Английский

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Visible‐Light Photoredox‐Catalyzed Remote Difunctionalizing Carboxylation of Unactivated Alkenes with CO₂

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(47), P. 21121 - 21128

Published: Aug. 4, 2020

Remote difunctionalization of unactivated alkenes is challenging but a highly attractive tactic to install two functional groups across long distances. Reported herein the first remote with CO2 . This visible-light photoredox catalysis strategy provides facile method synthesize series carboxylic acids bearing valuable fluorine- or phosphorus-containing groups. Moreover, this versatile protocol shows mild reaction conditions, broad substrate scope, and good functional-group tolerance. Based on DFT calculations, radical adds an alkene smoothly form new carbon radical, followed by 1,5-hydrogen atom-transfer process, rate-limiting step, generating more stable benzylic radical. The reduction radicals IrII species generates corresponding carbanions as key intermediates, which further undergo nucleophilic attack generate carboxylates.

Language: Английский

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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, Journal Year: 2019, Volume and Issue: 58(47), P. 17068 - 17073

Published: Sept. 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.

Language: Английский

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

Nature Catalysis, Journal Year: 2020, Volume and Issue: 3(11), P. 951 - 958

Published: Oct. 19, 2020

Language: Английский

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Beyond Carbon: Enantioselective and Enantiospecific Reactions with Catalytically Generated Boryl- and Silylcopper Intermediates

ACS Central Science, Journal Year: 2020, Volume and Issue: 6(7), P. 1070 - 1081

Published: July 9, 2020

Catalytic asymmetric C–C bond formation with alkylcopper intermediates as carbon nucleophiles is now textbook chemistry. Related chemistry boron and silicon where the boryl- accordingly silylcopper are catalytically regenerated from bench-stable pronucleophiles had been underdeveloped for years or did not even exist until recently. Over past decade, copper catalysis employing those main-group elements rapidly transformed into a huge field in its own right an impressive breadth of enantioselective C–B C–Si bond-forming reactions, respectively. Its current state art does have to shy away comparison that boron's silicon's common neighbor periodic table, carbon. This Outlook meant be detailed summary manifold advances. It rather aims at providing brief conceptual what forms basis latest exciting progress, especially area three-component reactions cross-coupling reactions.

Language: Английский

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Saturated Boronic Acids, Boronates, and Trifluoroborates: An Update on Their Synthetic and Medicinal Chemistry

Chemistry - A European Journal, Journal Year: 2021, Volume and Issue: 27(62), P. 15277 - 15326

Published: Sept. 9, 2021

Abstract This review discusses recent advances in the chemistry of saturated boronic acids, boronates, and trifluoroborates. Applications title compounds design boron‐containing drugs are surveyed, with special emphasis on α‐amino derivatives. A general overview as modern tools to construct C(sp 3 )−C )‐heteroatom bonds is given, including developments Suzuki‐Miyaura Chan‐Lam cross‐couplings, single‐electron‐transfer processes metallo‐ organocatalytic photoredox reactions, transformations boron “ate” complexes. Finally, an attempt summarize current state art synthesis trifluoroborates made, a brief mention “classical” methods (transmetallation organolithium/magnesium reagents species, anti‐Markovnikov hydroboration alkenes, modification alkenyl compounds) focus methodologies (boronation alkyl (pseudo)halides, derivatives carboxylic alcohols, primary amines, boronative C−H activation, novel approaches alkene hydroboration, 1,2‐metallate‐type rearrangements).

Language: Английский

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