Metallaphotoredox: The Merger of Photoredox and Transition Metal Catalysis

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 1485 - 1542

Published: Nov. 18, 2021

The merger of photoredox catalysis with transition metal catalysis, termed metallaphotoredox has become a mainstay in synthetic methodology over the past decade. Metallaphotoredox combined unparalleled capacity for bond formation broad utility photoinduced electron- and energy-transfer processes. Photocatalytic substrate activation allowed engagement simple starting materials metal-mediated bond-forming Moreover, electron or energy transfer directly key organometallic intermediates provided novel modes entirely complementary to traditional catalytic platforms. This Review details contextualizes advancements molecule construction brought forth by metallaphotocatalysis.

Language: Английский

---

Direct Photocatalyzed Hydrogen Atom Transfer (HAT) for Aliphatic C–H Bonds Elaboration

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 1875 - 1924

Published: Aug. 6, 2021

Direct photocatalyzed hydrogen atom transfer (d-HAT) can be considered a method of choice for the elaboration aliphatic C–H bonds. In this manifold, photocatalyst (PCHAT) exploits energy photon to trigger homolytic cleavage such bonds in organic compounds. Selective bond may achieved by judicious abstractor (key parameters are electronic character and molecular structure), as well reaction additives. Different classes PCsHAT available, including aromatic ketones, xanthene dyes (Eosin Y), polyoxometalates, uranyl salts, metal-oxo porphyrin tris(amino)cyclopropenium radical dication. The processes (mainly C–C formation) most cases carried out under mild conditions with help visible light. aim review is offer comprehensive survey synthetic applications d-HAT.

Language: Английский

---

Photocatalytic Late-Stage C–H Functionalization

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(8), P. 4237 - 4352

Published: Jan. 24, 2023

The emergence of modern photocatalysis, characterized by mildness and selectivity, has significantly spurred innovative late-stage C–H functionalization approaches that make use low energy photons as a controllable source. Compared to traditional strategies, photocatalysis paves the way toward complementary and/or previously unattainable regio- chemoselectivities. Merging compelling benefits with workflow offers potentially unmatched arsenal tackle drug development campaigns beyond. This Review highlights photocatalytic strategies small-molecule drugs, agrochemicals, natural products, classified according targeted bond newly formed one. Emphasis is devoted identifying, describing, comparing main mechanistic scenarios. draws critical comparison between established ionic chemistry photocatalyzed radical-based manifolds. aims establish current state-of-the-art illustrate key unsolved challenges be addressed in future. authors aim introduce general readership functionalization, specialist practitioners evaluation methodologies, potential for improvement, future uncharted directions.

Language: Английский

---

Catalytic three-component dicarbofunctionalization reactions involving radical capture by nickel

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(19), P. 10836 - 10856

Published: Jan. 1, 2021

The catalytic dicarbofunctionalization of unsaturated π bonds represents a powerful platform for the rapid construction complex motifs. Despite remarkable progress, novel and efficient methods achieving such transformations under milder conditions with chemo-, regio-, stereoselectivity still remain significant challenge; thus, their development is highly desirable. Recently, merging nickel catalysis radical chemistry offers new benign unprecedented reactivity selectivity. In this review, we summarize recent advances in area by underpinning domino involving capture to provide clear overview reaction designs mechanistic scenarios.

Language: Английский

---

Photochemical C–F Activation Enables Defluorinative Alkylation of Trifluoroacetates and -Acetamides

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(47), P. 19648 - 19654

Published: Nov. 18, 2021

The installation of gem-difluoromethylene groups into organic structures remains a daunting synthetic challenge despite their attractive structural, physical, and biochemical properties. A very efficient retrosynthetic approach would be the functionalization single C–F bond from trifluoromethyl group. Recent advances in this line attack have enabled activation trifluoromethylarenes, but limit accessible motifs to only benzylic gem-difluorinated scaffolds. In contrast, trifluoroacetates enable use as bifunctional synthon. Herein, we report photochemically mediated method for defluorinative alkylation commodity feedstock: ethyl trifluoroacetate. novel mechanistic was identified using our previously developed diaryl ketone HAT catalyst hydroalkylation diverse suite alkenes. Furthermore, electrochemical studies revealed that more challenging radical precursors, namely trifluoroacetamides, could also functionalized via synergistic Lewis acid/photochemical activation. Finally, concise gem-difluoro analogs FDA-approved pharmaceutical compounds.

Language: Английский

---

Dicarbofunctionalization of [1.1.1]Propellane Enabled by Nickel/Photoredox Dual Catalysis: One-Step Multicomponent Strategy for the Synthesis of BCP-Aryl Derivatives

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(28), P. 12961 - 12969

Published: July 6, 2022

Bicyclo[1.1.1]pentane (BCP) motifs as para-disubstituted aryl bioisosteres are playing an emerging role in pharmaceutical, agrochemical, and materials chemistry. The vast majority of these structures is obtained from a BCP electrophile or nucleophile, which themselves derived [1.1.1]propellane via cleavage the internal C–C bond through addition either radicals metal-based nucleophiles. Compared with current stepwise approaches, multicomponent reaction that provides direct access to complex diverse disubstituted products would be more attractive. Herein, we report single-step, approach synthetically versatile arylated nickel/photoredox catalysis. Importantly, this three-component process allows two bonds formed single step sets three quaternary centers, unprecedented any previously reported methods. method has been demonstrated allow architectures halide radical precursor substrates.

Language: Английский

---

Carbon-centered radical capture at nickel(II) complexes: Spectroscopic evidence, rates, and selectivity

Chem, Journal Year: 2023, Volume and Issue: 9(5), P. 1295 - 1308

Published: March 13, 2023

Language: Английский

---

Dual Nickel/Photoredox-Catalyzed Asymmetric Carbosulfonylation of Alkenes

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(23), P. 12532 - 12540

Published: May 30, 2023

An asymmetric three-component carbosulfonylation of alkenes is presented here. The reaction, involving the simultaneous formation a C-C and C-S bond across π-system, uses dual nickel/photoredox catalytic system to produce both β-aryl β-alkenyl sulfones in high yields with excellent levels stereocontrol (up 99:1 er). This protocol exhibits broad substrate scope functional group tolerance its synthetic potential has been demonstrated by successful applications toward pharmacologically relevant molecules. A array control experiments supports involvement secondary alkyl radical intermediate generated through addition sulfonyl double bond. Moreover, stoichiometric cross-over further suggest an underlying Ni(0)/Ni(I)/Ni(III) pathway operative these transformations.

Language: Английский

---

Enantioselective C(sp³)–H Functionalization of Oxacycles via Photo-HAT/Nickel Dual Catalysis

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(9), P. 5231 - 5241

Published: Feb. 22, 2023

The selective functionalization of ubiquitous but inert C-H bonds is highly appealing in synthetic chemistry, the direct transformation hydrocarbons lacking directing groups into high-value chiral molecules remains a formidable challenge. Herein, we develop an enantioselective C(sp3)-H undirected oxacycles via photo-HAT/nickel dual catalysis. This protocol provides practical platform for rapid construction and enantiomerically enriched directly from simple abundant hydrocarbon feedstocks. utility this strategy further demonstrated late-stage natural products synthesis many pharmaceutically relevant molecules. Experimental density functional theory calculation studies provide detailed insights mechanism origin enantioselectivity asymmetric functionalization.

Language: Английский

---

Nickel-catalysed enantioselective alkene dicarbofunctionalization enabled by photochemical aliphatic C–H bond activation

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(6), P. 655 - 665

Published: April 29, 2024

Abstract The development of novel strategies to rapidly construct complex chiral molecules from readily available feedstocks is a long-term pursuit in the chemistry community. Radical-mediated alkene difunctionalizations represent an excellent platform towards this goal. However, asymmetric versions remain highly challenging, and more importantly, examples featuring simple hydrocarbons as reaction partners are elusive. Here we report three-component dicarbofunctionalization capitalizing on direct activation C( sp 3 )–H bonds through combination photocatalysed hydrogen atom transfer nickel catalysis. This protocol provides efficient for installing two vicinal carbon–carbon across alkenes atom-economic fashion, providing wide array high-value α-aryl/alkenyl carbonyls phosphonates, well 1,1-diarylalkanes ubiquitous alkane, ether alcohol feedstocks. method exhibits operational simplicity, broad substrate scope regioselectivity, chemoselectivity enantioselectivity. compatibility with bioactive motifs expedient synthesis pharmaceutically relevant highlight synthetic potential protocol.

Language: Английский

---