Understanding mechanism driven regioselectivity in zirconium-catalysed hydroaminoalkylation: homoallylic amines from conjugated dienes

Chemical Science, Journal Year: 2024, Volume and Issue: 15(27), P. 10571 - 10576

Published: Jan. 1, 2024

The unexpected 4,1-hydroaminoalkylation of dienes provides selective access to linear homoallylic amines by zirconium catalysis. This switch from the traditional branched preferred regioselectivity product formation using this early transition metal can be attributed π-allyl intermediates. reactivity these isolated intermediates on a sterically accessible and coordinatively flexible chelating bis(ureate) Zr(iv) complex confirmed reversible C-C bond in hydroaminoalkylation

Language: Английский

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Recent Advances in Saturated N-Heterocycle C–H Bond Functionalization for Alkylated N-Heterocycle Synthesis

Synthesis, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 1, 2024

Abstract The prominence of saturated N-heterocycle motifs in pharmaceuticals is undeniable. Challenges associated with the alkylation scaffolds to efficiently access new drug analogues are hampered by synthetically laborious routes. Stereocontrolled alkyl-substitutions onto N-heterocycles particularly difficult high yields traditional synthetic methods. Alternatively, C–H bond functionalization provides a and powerful avenue directly selectively functionalizing/alkylating/ arylating abundantly available bonds N-heterocycles. This review highlights complementary methods for activating functionalizing chemo-, regio-, or stereoselectively alkylated products. challenge has required catalyst development useful N-heterocyclic building blocks late-stage functionalization. Early transition metal, late photoredox, electrochemical discussed. selective α, β, γ form C–C, C–N, C–O, C–B presented. 1 Introduction 2 Transition Metal Catalyzed α-Alkylation 3 Late α-Functionalization 4 Photoredox-Catalyzed 5 Electrochemical 6 Functionalization β Bonds 7 Conclusions/Outlook

Language: Английский

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Catalytic Installation of Primary Amines Onto Polyolefins for Oligomer Valorization

Macromolecular Rapid Communications, Journal Year: 2024, Volume and Issue: 45(23)

Published: Oct. 1, 2024

Polymerization of primary amine-containing monomers is challenging because the amine inhibits polymerization catalyst activity. An alternative approach to access functionalized polymers postpolymerization modification. To this end, hydroaminoalkylation vinyl-terminated polyolefins with N-(trimethylsilyl)benzylamine used prepare amine-terminated polyolefins, free substituent being revealed upon hydrolytic work up. These materials are spectroscopically characterized, and an investigation thermal properties by differential scanning calorimetry thermogravimetric analysis completed. results show that increases glass transition temperature improves stability. The reactive functionality in photo-oxidative dimerization demonstrate how elusive can be applied oligomer valorization.

Language: Английский

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Exploiting natural complexity for substrate controlled regioselectivity and stereoselectivity in tantalum catalysed hydroaminoalkylation

Green Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Naturally occurring and structurally diverse alkene-containing substrates, terpenes, provided a platform for establishing chemo-, regio-, diastereoselective reactivity in tantalum catalysed hydroaminoalkylation.

Language: Английский

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Tantalum Catalyzed Hydroaminoalkylation Enables a Telescoping Catalytic Reaction Sequence for the Synthesis of Benzoannulated Indolizidines and Quinolizidines

Organometallics, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 12, 2024

Language: Английский

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