Co‐Catalyzed Reductive Cross‐Couplings of Csp3−S with Callyl−O Electrophiles to form Csp3−Csp3 Bonds DOI
Mengyu Gao, Corinne Gosmini

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(21), С. 3597 - 3602

Опубликована: Сен. 7, 2023

Abstract Cross‐electrophilic coupling of various benzyl sulfonium salts with C allyl −O electrophiles is described using a simple Co−Mn catalytic system. This system able to activate both the stable sp 3 −S bond and allylic acetate or ether under mild reaction conditions form functionalized alkyl olefinic compounds. Allyl methyl ethers were employed for first time in transition metal‐catalyzed cross‐electrophilic build −C bonds. Preliminary mechanistic studies suggested involvement radicals generated from C−S cleavage through single electron transfer.

Язык: Английский

Skeletal Editing Approach to Bridge-Functionalized Bicyclo[1.1.1]pentanes from Azabicyclo[2.1.1]hexanes DOI
Brandon A. Wright, Anastassia Matviitsuk, Michael J. Black

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(20), С. 10960 - 10966

Опубликована: Май 5, 2023

Azabicyclo[2.1.1]hexanes (aza-BCHs) and bicyclo[1.1.1]pentanes (BCPs) have emerged as attractive classes of sp3-rich cores for replacing flat, aromatic groups with metabolically resistant, three-dimensional frameworks in drug scaffolds. Strategies to directly convert, or "scaffold hop", between these bioisosteric subclasses through single-atom skeletal editing would enable efficient interpolation within this valuable chemical space. Herein, we describe a strategy hop" aza-BCH BCP nitrogen-deleting edit. Photochemical [2+2] cycloadditions, used prepare multifunctionalized frameworks, are coupled subsequent deamination step afford bridge-functionalized BCPs, which few synthetic solutions currently exist. The modular sequence provides access various privileged bridged bicycles pharmaceutical relevance.

Язык: Английский

Процитировано

77
Mechanistic Investigation of Ni-Catalyzed Reductive Cross-Coupling of Alkenyl and Benzyl Electrophiles DOI Creative Commons
Raymond F. Turro, Julie L. Hofstra Wahlman, Zhengjia Tong

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(27), С. 14705 - 14715

Опубликована: Июнь 26, 2023

Mechanistic investigations of the Ni-catalyzed asymmetric reductive alkenylation

Язык: Английский

Процитировано

49
Control of Redox‐Active Ester Reactivity Enables a General Cross‐Electrophile Approach to Access Arylated Strained Rings** DOI
Daniel C. Salgueiro, K. Benjamin, Ilia A. Guzei

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(33)

Опубликована: Июнь 11, 2022

Strained rings are increasingly important for the design of pharmaceutical candidates, but cross-coupling strained remains challenging. An attractive, underdeveloped, approach to diverse functionalized carbocyclic and heterocyclic frameworks containing all-carbon quaternary centers is coupling abundant strained-ring carboxylic acids with aryl halides. Herein we disclose development a nickel-catalyzed cross-electrophile that couples variety ring N-hydroxyphthalimide (NHP) esters, derived from acid in one step, various heteroaryl halides under reductive conditions. The chemistry enabled by discovery methods control NHP ester reactivity, tuning solvent or using modified

Язык: Английский

Процитировано

56
A General and Practical Route to Functionalized Bicyclo[1.1.1]Pentane‐Heteroaryls Enabled by Photocatalytic Multicomponent Heteroarylation of [1.1.1]Propellane DOI
Weichen Huang, Sebastian Keeß,

Gary A. Molander

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(24)

Опубликована: Апрель 15, 2023

Abstract 1‐Aryl‐substituted bicyclo[1.1.1]pentanes (BCPs) are an important class of BCP derivatives with widespread application in drug development. Most syntheses these materials require multiple chemical steps via electrophiles or nucleophiles derived from [1.1.1]propellane. Although one‐step, multicomponent radical cross‐coupling reactions could provide a more sustainable and rapid route to access diverse heteroarylated BCPs, current approaches limited tertiary alkyl radicals, leading decrease their practical value. In this study, conceptually different approach enabled by heteroarylation [1.1.1]propellane functionalized BCPs is described. Importantly, protocol compatible primary‐, secondary‐, aliphatic as well various fluoroalkyl sources, thus enabling library generation sought‐after for

Язык: Английский

Процитировано

36
Decarboxylative, Radical C–C Bond Formation with Alkyl or Aryl Carboxylic Acids: Recent Advances DOI Creative Commons
Joshua D. Tibbetts, Alexander J. Cresswell,

Hannah E. Askey

и другие.

Synthesis, Год журнала: 2023, Номер 55(20), С. 3239 - 3250

Опубликована: Апрель 26, 2023

Abstract The ubiquity of carboxylic acids as naturally derived or man-made chemical feedstocks has spurred the development powerful, decarboxylative C–C bond-forming transformations for organic synthesis. Carboxylic benefit not only from extensive commercial availability, but are stable surrogates organohalides organometallic reagents in transition-metal-catalysed cross-coupling. Open shell reactivity (or derivatives thereof) to furnish carbon-centred radicals is proving transformative synthetic chemistry, enabling novel and strategy-level C(sp3)–C bond disconnections with exquisite chemoselectivity. This short review will summarise several latest advances this ever-expanding area. 1 Introduction 2 Improved Decarboxylative Arylations 3 sp3–sp3 Cross-Coupling Acids Aliphatic Bromides 4 Alcohols Amines 5 Doubly 6 Bond Formation (Hetero)aryl 7 Conclusions

Язык: Английский

Процитировано

25
Simplified Modular Access to Enantiopure 1,2-Aminoalcohols via Ni-Electrocatalytic Decarboxylative Arylation DOI Creative Commons

Jiawei Sun,

Hirofumi Endo,

Megan A. Emmanuel

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(9), С. 6209 - 6216

Опубликована: Фев. 22, 2024

Chiral aminoalcohols are omnipresent in bioactive compounds. Conventional strategies to access this motif involve multiple-step reactions install the requisite functionalities stereoselectively using conventional polar bond analysis. This study reveals that a simple chiral oxazolidine-based carboxylic acid can be readily transformed substituted with high stereochemical control by Ni-electrocatalytic decarboxylative arylation. general, robust, and scalable coupling used synthesize variety of medicinally important compounds, avoiding protecting functional group manipulations, thereby dramatically simplifying their preparation.

Язык: Английский

Процитировано

14
Nickel‐Electrocatalytic Decarboxylative Arylation to Access Quaternary Centers** DOI
Gabriele Laudadio, Philipp Neigenfind, Áron Péter

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(8)

Опубликована: Янв. 5, 2024

Abstract There is a pressing need, particularly in the field of drug discovery, for general methods that will enable direct coupling tertiary alkyl fragments to (hetero)aryl halides. Herein uniquely powerful and simple set conditions achieving this transformation with unparalleled generality chemoselectivity disclosed. This new protocol placed context other recently reported methods, applied simplify routes known bioactive building blocks molecules, scaled up both batch flow. The role pyridine additive as well mechanism reaction are interrogated through Cyclic Voltammetry studies, titration experiments, control reactions Ni(0) Ni(II)‐complexes, ligand optimization data. Those studies indicate formation BINAPNi(0) minimized an active pyridine‐stabilized Ni(I) species sustained during reaction. Our preliminary mechanistic ruled out involvement electrochemical cross‐coupling, which mediated by via Ni(I)‐Ni(II)‐Ni(III)‐Ni(I) catalytic cycle.

Язык: Английский

Процитировано

11
Cross-Electrophile Coupling: Principles, Methods, and Applications in Synthesis DOI Creative Commons
Lauren E. Ehehalt, Omar M. Beleh, Isabella C. Priest

и другие.

Chemical Reviews, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 26, 2024

Cross-electrophile coupling (XEC), defined by us as the cross-coupling of two different σ-electrophiles that is driven catalyst reduction, has seen rapid progression in recent years. As such, this review aims to summarize field from its beginnings up until mid-2023 and provide comprehensive coverage on synthetic methods current state mechanistic understanding. Chapters are split type bond formed, which include C(sp

Язык: Английский

Процитировано

10
Nickel-mediated alkyl-, acyl-, and sulfonylcyanation of [1.1.1]propellane DOI Creative Commons
Weizhe Dong, Sebastian Keeß,

Gary A. Molander

и другие.

Chem Catalysis, Год журнала: 2023, Номер 3(5), С. 100608 - 100608

Опубликована: Апрель 19, 2023

Язык: Английский

Процитировано

19
Nickel-Catalyzed Electroreductive Coupling of Alkylpyridinium Salts and Aryl Halides DOI
Jiantao Fu,

Windsor Lundy,

Rajdip Chowdhury

и другие.

ACS Catalysis, Год журнала: 2023, Номер 13(14), С. 9336 - 9345

Опубликована: Июнь 28, 2023

An electrochemical, nickel-catalyzed reductive coupling of alkylpyridinium salts and aryl halides is reported. High-throughput experimentation (HTE) was employed for rapid reaction optimization evaluation a broad scope pharmaceutically relevant structurally diverse halides, including complex drug-like substrates. In addition, the transformation compatible with both primary secondary distinct conditions. Mechanistic insights were critical to enhance efficiency using salts. Systematic comparisons electrochemical non-electrochemical methods revealed complementary two approaches.

Язык: Английский

Процитировано

18