Nickel‐Catalyzed Switchable Site‐Selective Alkene Hydroalkylation by Temperature Regulation**

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(31)

Published: May 25, 2022

Regiodivergent alkene functionalization that produces either regioisomer starting from the same raw materials is desirable. Herein, we report a nickel-catalyzed switchable site-selective hydroalkylation. The selection of reaction temperatures leads to protocols provide regiodivergent hydroalkylated products single substrate. This protocol allows convenient synthesis α- and β-branched protected amines, both which are important fields pharmaceutical chemistry biochemistry. In addition, enantioenriched alkylamines can be accessed in catalytic asymmetric variant. Preliminary mechanistic studies indicate formation more stable nickelacycle provides driving force migration. thermodynamic kinetic properties different reduction elimination intermediates responsible for site-selectivity.

Language: Английский

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Orthogonal Regulation of Nucleophilic and Electrophilic Sites in Pd‐Catalyzed Regiodivergent Couplings between Indazoles and Isoprene

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(15), P. 8321 - 8328

Published: Jan. 19, 2021

Abstract Depending on the reactant property and reaction mechanism, one major regioisomer can be favored in a that involves multiple active sites. Herein, an orthogonal regulation of nucleophilic electrophilic sites regiodivergent hydroamination isoprene with indazoles is demonstrated. Under Pd‐hydride catalysis, 1,2‐ or 4,3‐insertion pathway respect to could controlled by choice ligands. In terms indazoles, occurs at either N 1 ‐ 2 ‐position governed acid co‐catalysts. Preliminary experimental studies have been performed rationalize mechanism regioselectivity. This study not only contributes practical tool for selective functionalization isoprene, but also provides guide manipulate regioselectivity ‐functionalization indazoles.

Language: Английский

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Recent advances in the synthesis of 1,1-diarylalkanes by transition-metal catalysis

Science China Chemistry, Journal Year: 2021, Volume and Issue: 64(4), P. 513 - 533

Published: Jan. 12, 2021

Language: Английский

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Catalytic Asymmetric Hydroalkylation of α,β-Unsaturated Amides Enabled by Regio-Reversed and Enantiodifferentiating syn-Hydronickellation

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(14), P. 8766 - 8773

Published: July 2, 2021

Here, we report an enantioselective nickel-hydride catalyzed hydroalkylation of readily accessible β-alkyl-α,β-unsaturated amides to form structurally diverse β-chiral amides. This process was proposed proceed through enantiodifferentiating syn-hydrometalation nickel hydride, forming chiral alkylnickel at the β-position in which regioselectivity is different from that with copper hydride. regio-reversed hydronickellation provides a complementary approach access enantioenriched β-functionalization stereocenter β-position.

Language: Английский

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Nickel-catalysed migratory hydroalkynylation and enantioselective hydroalkynylation of olefins with bromoalkynes

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: June 18, 2021

Abstract α-Chiral alkyne is a key structural element of many bioactive compounds, chemical probes, and functional materials, valuable synthon in organic synthesis. Here we report NiH-catalysed reductive migratory hydroalkynylation olefins with bromoalkynes that delivers the corresponding benzylic alkynylation products high yields excellent regioselectivities. Catalytic enantioselective styrenes has also been realized using simple chiral PyrOx ligand. The obtained enantioenriched alkynes are versatile synthetic intermediates can be readily transformed into synthetically useful synthons.

Language: Английский

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