New Strategies for the Transition-Metal Catalyzed Synthesis of Aliphatic Amines

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(5), P. 2613 - 2692

Published: Feb. 17, 2020

Transition-metal catalyzed reactions that are able to construct complex aliphatic amines from simple, readily available feedstocks have become a cornerstone of modern synthetic organic chemistry. In light the ever-increasing importance across range chemical sciences, this review aims provide concise overview transition-metal approaches alkylamine synthesis and their functionalization. Selected examples amine bond forming include: (a) hydroamination hydroaminoalkylation, (b) C(sp3)–H functionalization, (c) visible-light-mediated photoredox catalysis.

Language: Английский

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C–H activation

Nature Reviews Methods Primers, Journal Year: 2021, Volume and Issue: 1(1)

Published: June 17, 2021

Language: Английский

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Cobalt-catalysed C–H methylation for late-stage drug diversification

Nature Chemistry, Journal Year: 2020, Volume and Issue: 12(6), P. 511 - 519

Published: May 29, 2020

Language: Английский

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Design and Optimization of Catalysts Based on Mechanistic Insights Derived from Quantum Chemical Reaction Modeling

Chemical Reviews, Journal Year: 2019, Volume and Issue: 119(11), P. 6509 - 6560

Published: May 8, 2019

Until recently, computational tools were mainly used to explain chemical reactions after experimental results obtained. With the rapid development of software and hardware technologies make modeling more reliable, they can now provide valuable insights even become predictive. In this review, we highlighted several studies involving predictions unexpected reactivities or providing mechanistic for organic organometallic that led improved results. Key these successful applications is an integration between theory experiment allows incorporation empirical knowledge with precise computed values. Computer already a standard tool being embraced by ever increasing group researchers, it clear its utility in predictive reaction design will increase further near future.

Language: Английский

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Dioxazolones: Stable Substrates for the Catalytic Transfer of Acyl Nitrenes

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(8), P. 4751 - 4769

Published: March 30, 2020

Dioxazolones are a convenient class of acyl nitrene transfer reagents. Their application in homogeneous transition-metal catalysis has led to many new amidation reactions. typically activated by transition metals at relatively low reaction temperatures. The metal nitrenoids formed decarboxylative activation dioxazolones generally electron deficient and commonly react concerted fashion. "Intermolecular" insertion reactions involving preactivated C–H bonds ("inner-sphere" mechanism) easily compete with the Curtius-type rearrangement, but for intramolecular "direct" transfer/insertion nonpreactivated substrates (i.e., without preceding formation metal–carbon or metal–hydride bonds) extensive ligand optimization is important prevent such unwanted side ease dioxazolone synthesis, CO2 gas as sole byproduct from dioxazolones, importance general development several interesting producing N-aryl amides, oxazoles, lactams. Since proceeds under mild conditions, stereo- enantioselective also possible, which useful synthesis bioactive nitrogen-containing compounds. This review provides an overview these reported recent years.

Language: Английский

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Ir-Catalyzed Intermolecular Branch-Selective Allylic C–H Amidation of Unactivated Terminal Olefins

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(6), P. 2268 - 2273

Published: Feb. 4, 2019

An efficient method for intermolecular branch-selective allylic C–H amidation has been accomplished via Ir(III) catalysis. The reaction proceeds through initial activation, supported by the isolation and crystallographic characterization of an allyl-Ir(III) intermediate, followed a subsequent oxidative with readily available dioxazolones as nitrenoid precursors. A diverse range amides are successfully installed at branched position terminal alkenes in good yields regioselectivities. Importantly, allows use amide-derived precursors avoiding problematic Curtius-type rearrangements.

Language: Английский

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Asymmetric formation of γ-lactams via C–H amidation enabled by chiral hydrogen-bond-donor catalysts

Nature Catalysis, Journal Year: 2019, Volume and Issue: 2(3), P. 219 - 227

Published: Feb. 18, 2019

Language: Английский

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Mechanism-Guided Development of Transition-Metal-Catalyzed C–N Bond-Forming Reactions Using Dioxazolones as the Versatile Amidating Source

Accounts of Chemical Research, Journal Year: 2021, Volume and Issue: 54(11), P. 2683 - 2700

Published: May 12, 2021

ConspectusCatalytic reactions that construct carbon–nitrogen bonds are one of central themes in both synthetic and medicinal chemistry since the obtainable nitrogen-containing motifs commonly encountered natural products have also seen a growing prominence as key structural features marketed drugs preclinical candidates. Pd-catalyzed cross-couplings, such Buchwald–Hartwig amination, at forefront methods practical settings. However, they require prefunctionalized substrates (hetero)aryl halides must be prepared independently, often by multiple operations. One emerging way to circumvent these preparatory steps directly convert ubiquitous C–H into valuable C–N is catalytic which allows chemists devise shorter more efficient retrosynthetic schemes. The past two decades witnessed considerable progress expanding repertoire this strategy, especially identifying effective amino group precursors. In context, dioxazolones experienced dramatic resurgence recent years versatile nitrogen source combination with transition-metal catalyst systems facilitate decarboxylation access metal-acylnitrenoid intermediates. addition their high robustness easy accessibility from abundant carboxylic acids, unique reactivity transient intermediates amido transfer has led fruitful journey for mild amidation reactions.This Account summarizes our contributions development bond-forming using nitrenoid precursors, categorized subsets according mechanistic differences: inner- versus outer-sphere pathways. first section describes how we could unveil potential realm inner-sphere amidation, where demonstrated serve not only manageable alternatives acyl azides but highly reagents significantly reduce loading temperature. Taking advantage conditions 9 Cp*M complexes (M = Rh, Ir, Co) or isoelectronic Ru species, dramatically expanded accessible scope. Mechanistic investigations revealed putative metal-nitrenoid species involved intermediate during catalysis, leads facile bond formation. On basis underpinning, succeeded developing novel platforms harness intermediacy metal-nitrenoids explore insertion via an pathway. Indeed, tailored catalysts were capable suppressing competitive Curtius-type decomposition, thus granting lactam products. We further repurposed upon modification chelating ligands identity transition metal achieve three goals: (i) addressing selectivity issues control regio-, chemo-, enantioselectivities, (ii) sustainable catalysis first-low metals, (iii) navigating chemical space (di)functionalization alkenes/alkynes. Together own research efforts, highlighted herein some important relevant advances other groups. finally conclude brief overview eye toward developments.

Language: Английский

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Nitrene transfer catalysts for enantioselective C–N bond formation

Nature Reviews Chemistry, Journal Year: 2021, Volume and Issue: 5(8), P. 580 - 594

Published: June 28, 2021

Language: Английский

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Iridium-Catalyzed Enantioselective C(sp³)–H Amidation Controlled by Attractive Noncovalent Interactions

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(17), P. 7194 - 7201

Published: April 12, 2019

While remarkable progress has been made over the past decade, new design strategies for chiral catalysts in enantioselective C(sp3)–H functionalization reactions are still highly desirable. In particular, ability to use attractive noncovalent interactions rate acceleration and enantiocontrol would significantly expand current arsenal asymmetric metal catalysis. Herein, we report development of a Ir(III)-catalyzed intramolecular amidation reaction dioxazolone substrates synthesis optically enriched γ-lactams using newly designed α-amino-acid-based ligand. This Ir-catalyzed proceeds with excellent efficiency outstanding enantioselectivity both activated unactivated alkyl bonds under very mild conditions. It offers first general route γ-alkyl γ-lactams. Water was found be unique cosolvent achieve γ-aryl lactam production. Mechanistic studies revealed that ligands form well-defined groove-type pocket around Ir center. The hydrophobic effect this allows facile stereocontrolled binding polar or aqueous media. Instead capitalizing on steric repulsions as conventional approaches, catalyst operates through an unprecedented mechanism nitrenoid C–H insertion featuring multiple interactions.

Language: Английский

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