tBuOK/DMSO/O2catalyzed direct α-C(sp3)–H alkylation with styrenes: productive α-amino radicals for hydroaminoalkylation DOI

Zhangqiang Yan,

Zhen Zhang, Tao Wen

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(11), P. 2714 - 2720

Published: Jan. 1, 2023

Direct α-C(sp 3 )–H alkylation of hydroaminoalkylation (HAA) catalyzed by t BuOK/DMSO/O 2 from α-aryl benzylamines with styrenes is reported.

Language: Английский

Regioselective Hydroaminoalkylation with Silylated Alkenes for β-Amino Acid Synthesis DOI

M. THOMPSON,

Decheng Yang, J. S. Higgins

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 8, 2025

Catalyst and substrate steric electronic features that influence regioselectivity in hydroaminoalkylation were leveraged to develop a synthetic approach for the selective synthesis of β-amino acids. An situ generated tantalum-ureate catalyst was used prepare 18 γ-silylated amines up 93% yield from internal silylated alkenes. β-Amino silane regioisomer production rarely observed, making this work one few examples highly regioselective with unsymmetric These γ-amino silanes converted alcohols modified Tamao-Fleming oxidation strategy followed by two additional steps acids, including key fragment anticancer drug candidate Ipatasertib.

Language: Английский

Citations

0
A General Protocol toward Synthesis of 3-Methylindoles Using Acenaphthoimidazolyidene-Ligated Oxazoline Palladacycle DOI

Ruoqian Fan,

Haili Wen,

Zhen Chen

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 26(1), P. 22 - 28

Published: Dec. 21, 2023

An efficient catalytic strategy toward the synthesis of N-substituted 3-methylindoles from inactive o-dihaloarenes and N-allylamines was developed by using a 1,3-bis(2,6-diisopropylphenyl)acenaphthoimidazol-2-ylidene (AnIPr)-ligated oxazoline palladacycle. It enabled very broad substrate scope tolerating different functional groups, electronic properties, steric bulkiness afforded desired products in good to excellent yields. Importantly, it showed great potential synthesize several bioactive compounds key intermediates natural high

Language: Английский

Citations

6
Stable Meisenheimer Complexes as Powerful Photoreductants Readily Obtained from Aza‐Heteroaromatic Compounds DOI Creative Commons
Francesco Calogero,

Leonie Wilczek,

Emanuele Pinosa

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(44)

Published: July 30, 2024

Abstract Excited states of radical anions derived from the photoreduction stable organic molecules are suggested to serve as potent reductants. However, excited these species too short‐lived allow bimolecular quenching processes. Recently, singlet state Meisenheimer complexes, which possess a long‐lived state, was identified competent for reduction challenging substrates (−2.63 V vs. SCE, saturated calomel electrode). To produce reasonably and simply accessible different addition n BuLi readily available aromatic heterocycles investigated, photoreactivity generated studied. In this paper, we present straightforward preparation family powerful photoreductants (*E ox < −3 SCE in their states, determined by DFT time‐dependent TD‐DFT calculations; DFT, density functional theory) that can induce dehalogenation electron‐rich aryl chlorides form C−C bond through cyclization. Photophysical analyses computational studies combination with experimental mechanistic investigations demonstrate ability adduct act strong electron donor under visible light irradiation.

Language: Английский

Citations

2
Recent Advances in Saturated N-Heterocycle C–H Bond Functionalization for Alkylated N-Heterocycle Synthesis DOI
Laurel L. Schafer, Cameron H. M. Zheng

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

Citations

1
Five-membered ring systems: pyrroles and benzo analogs DOI
Justin M. Lopchuk

Progress in heterocyclic chemistry, Journal Year: 2023, Volume and Issue: unknown, P. 199 - 250

Published: Jan. 1, 2023

Language: Английский

Citations

1
Stable Meisenheimer Complexes as Powerful Photoreductants Readily Obtained from Aza‐Heteroaromatic Compounds DOI Creative Commons
Francesco Calogero,

Leonie Wilczek,

Emanuele Pinosa

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(44)

Published: July 30, 2024

Abstract Excited states of radical anions derived from the photoreduction stable organic molecules are suggested to serve as potent reductants. However, excited these species too short‐lived allow bimolecular quenching processes. Recently, singlet state Meisenheimer complexes, which possess a long‐lived state, was identified competent for reduction challenging substrates (−2.63 V vs. SCE, saturated calomel electrode). To produce reasonably and simply accessible different addition n BuLi readily available aromatic heterocycles investigated, photoreactivity generated studied. In this paper, we present straightforward preparation family powerful photoreductants (*E ox < −3 SCE in their states, determined by DFT time‐dependent TD‐DFT calculations; DFT, density functional theory) that can induce dehalogenation electron‐rich aryl chlorides form C−C bond through cyclization. Photophysical analyses computational studies combination with experimental mechanistic investigations demonstrate ability adduct act strong electron donor under visible light irradiation.

Language: Английский

Citations

0
Exploiting natural complexity for substrate controlled regioselectivity and stereoselectivity in tantalum catalysed hydroaminoalkylation DOI
Cameron H. M. Zheng, Ben E. Nadeau, Heather L. Trajano

et al.

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

Citations

0
Tantalum Catalyzed Hydroaminoalkylation Enables a Telescoping Catalytic Reaction Sequence for the Synthesis of Benzoannulated Indolizidines and Quinolizidines DOI
Cameron H. M. Zheng,

Carla A. Esslinger,

O Dressler

et al.

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

Published: Sept. 12, 2024

Language: Английский

Citations

0
tBuOK/DMSO/O2catalyzed direct α-C(sp3)–H alkylation with styrenes: productive α-amino radicals for hydroaminoalkylation DOI

Zhangqiang Yan,

Zhen Zhang, Tao Wen

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(11), P. 2714 - 2720

Published: Jan. 1, 2023

Direct α-C(sp 3 )–H alkylation of hydroaminoalkylation (HAA) catalyzed by t BuOK/DMSO/O 2 from α-aryl benzylamines with styrenes is reported.

Language: Английский

Citations

0