Palladium-Catalyzed Allylation of Endocyclic 1-Azaallyl Anions DOI
Xiaoyu Yang, Biao Zhang,

Junhao Ruan

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(12), P. 8896 - 8905

Published: June 10, 2024

Endocyclic 1-azaallyl anions engage allyl acetates in a palladium-catalyzed allylation followed by reduction to give unprotected 2-(hetero)aryl-3-allylpiperidines and 2-allyl-3-arylmorpholines, products not easily accessible other means. The group is then readily transformed into variety of functional groups. Preliminary studies on the asymmetric variant reaction using an enantiomerically pure BI-DIME-type ligand provide product with moderate enantioselectivity. Computational suggest that energy barriers inner-sphere reductive elimination outer-sphere nucleophilic substitution are almost same, which makes both them possible pathways. In addition, mechanism displays enantiodiscriminating C–C bond forming step, while much less selective, combined

Language: Английский

Copper-Catalyzed Yne-Allylic Substitutions Using Stabilized Nucleophiles DOI

Shengtong Niu,

Yingkun Luo,

Chao Xu

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(12), P. 6840 - 6850

Published: May 25, 2022

Using stabilized "soft" nucleophiles in copper-catalyzed allylic substitutions is highly desirable but remains an unsolved challenge for the last 40 years. In this work, a general protocol of using such as indoles, pyrroles, amines, and 1,3-dicarbonyls has been developed, delivering large variety functionalized 1,3- 1,4-enynes with high levels regio- stereoselectivities (67 examples). A range further transformations products can be easily achieved to release various molecules. mechanistic rationale copper acetylide-bonded cation key intermediate that features outer-sphere nucleophilic attack proposed. Additionally, series diversified reactivities have demonstrated, which will inspire studies.

Language: Английский

Citations

41
Cobalt-Catalyzed Diastereo- and Enantioselective Carbon–Carbon Bond Forming Reactions of Cyclobutenes DOI

Zhikun Liang,

Lei Wang, Yu Wang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(6), P. 3588 - 3598

Published: Feb. 3, 2023

Catalytic enantioselective functionalization of cyclobutenes constitutes a general and modular strategy for construction enantioenriched complex cyclobutanes bearing multiple stereogenic centers, as chiral four-membered rings are common motifs in biologically active molecules versatile intermediates organic synthesis. However, synthesis through such remained significantly limited. Herein, we report series unprecedented cobalt-catalyzed carbon-carbon bond forming reactions that initiated carbometalation. The protocols feature diastereo- introduction allyl, alkynyl, functionalized alkyl groups. Mechanistic studies indicated an unusual 1,3-cobalt migration subsequent β-carbon elimination cascade process occurred the allyl addition. These new discoveries established elementary cobalt catalysis extension diversity nucleophiles transformations cyclobutenes.

Language: Английский

Citations

31
Facile Access to Quaternary Carbon Centers via Ni-Catalyzed Arylation of Alkenes with Organoborons DOI
Zi-Chao Wang, Lei Gao, Songyang Liu

et al.

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

Published: Jan. 16, 2025

Quaternary carbon centers are widespread structural motifs, thus representing extensive interest in organic synthesis. We describe here an efficient nickel-catalyzed intermolecular, Markovnikov-selective arylation of minimally functionalized alkenes with stable organoborons, affording a broad range cyclic or acyclic quaternary under mild conditions. The utilization the diimine ligand is critical for high reactivity and chemoselectivity. Furthermore, using bulky chiral as Ni catalyst, stereocenters can be readily prepared levels enantiocontrol. Mechanism studies suggest that, before protonation, rare nickel shift from alkyl to aryl might occur.

Language: Английский

Citations

1
Nickel-Catalyzed Carbonylation of Cyclopropanol with Benzyl Bromide for Multisubstituted Cyclopentenone Synthesis DOI

Liting Hou,

Wenyi Huang,

Xianqing Wu

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(14), P. 2699 - 2704

Published: April 7, 2022

Herein, we reported a Ni-catalyzed carbonylation of cyclopropanol with benzyl bromide to afford multisubstituted cyclopentenone under 1 atm CO. The reaction proceeds through cascade bromides, followed by generation nickel homoenolate from cyclopropanols via β-C elimination 1,4-diketones, which undergoes intramolecular Aldol condensation furnish highly substituted derivatives in moderate good yields. exhibits high functional group tolerance broad substrate scope.

Language: Английский

Citations

30
Copper-catalyzed asymmetric allylic substitution of racemic/meso substrates DOI Creative Commons
Jun Li, Junrong Huang, Yan Wang

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(22), P. 8280 - 8294

Published: Jan. 1, 2024

The synthesis of enantiomerically pure compounds is a pivotal subject in the field chemistry, with enantioselective catalysis currently standing as primary approach for delivering specific enantiomers. Among these strategies, Cu-catalyzed asymmetric allylic substitution (AAS) significant and irreplaceable, especially when it comes to use non-stabilized nucleophiles (pK > 25). Although AAS prochiral substrates has also been widely developed, methodologies involving racemic/meso are highly desirable, undergo dynamic processes give single enantiomer products. Inspired by pioneering work Alexakis, Feringa Gennari groups, continuously employed deracemization desymmetrization enriched In this review, we mainly focus on developments over past two decades, providing an explicit outline ligands employed, scope nucleophiles, underlying their practical applications.

Language: Английский

Citations

8
Visible-light-induced tandem ring opening/1,6-conjugate addition of cyclobutanols with p-quinone methides under metal- and additive-free conditions DOI

Tongyao Zhou,

Jie Zeng, Yang Liu

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(3), P. 1375 - 1380

Published: Jan. 1, 2024

A visible-light-mediated tandem ring opening/1,6-conjugate addition of cyclobutanols with p -quinone methides was developed. This protocol allowed the formation δ,δ-diaryl ketones in presence a readily available organic photocatalyst.

Language: Английский

Citations

5
Ring‐Opening Cross‐Coupling/Cyclization Reaction of Cyclopropanols with Organic Compounds DOI
Fatemeh Doraghi,

Seyedeh Pegah Aledavoud,

Azadeh Fakhrioliaei

et al.

ChemistrySelect, Journal Year: 2023, Volume and Issue: 8(32)

Published: Aug. 23, 2023

Abstract Cyclopropanols, due to their particular chemistry, can participate in various synthetic reactions with retention or cleavage of the strained three‐membered ring. Direct cross‐coupling ring‐opening reaction such molecules access organic compounds, as ketones has great importance medicinal chemistry and material sciences. Hence, coupling reaction/cyclization cyclopropanols for constructing new valuable presence a transition metal catalyst under metal‐free conditions is described this context. The features are discussed, mechanisms challenging highlighted.

Language: Английский

Citations

12
Synthesis of pyranopyrazoles with a chiral quaternary carbon stereocenter via copper-catalyzed enantioselective [3 + 3] cycloaddition DOI

Meihui Wang,

Bo Li,

Baihui Gong

et al.

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(17), P. 2850 - 2853

Published: Jan. 1, 2022

A copper-catalyzed enantioselective [3 + 3] cycloaddition of propargyl carbonates and pyrazolones has been disclosed. This reaction provided an efficient route to synthesize pyranopyrazoles containing a chiral quaternary carbon stereocenter in good yields with excellent enantioselectivities. In addition, the hydroxyl group products could be conveniently transformed into variety functional groups, such as aldehyde, nitrile, alkene, ester amide which further increased synthetic value this reaction.

Language: Английский

Citations

18
Recent Advances in Non-Precious Metal Catalysis DOI
Hao Wu, Bo Qu, Thach T. Nguyen

et al.

Organic Process Research & Development, Journal Year: 2022, Volume and Issue: 26(8), P. 2281 - 2310

Published: Aug. 2, 2022

This review provides a summary of recently published developments in the field nonprecious metal catalysis (NPMC) and highlights range synthetic applications captured research between July October 2021. is an installment series on this area briefing Ni, Cu, Fe, Co catalysis. There has been evident increase publications NPMC, which indicates widespread interest among laboratories academia industry development utilization catalytic these metals.

Language: Английский

Citations

18
Arylation of Cyclopropanol with Pyrrole: Asymmetric Synthesis of Indolizidine 167B, Indolizidine 209D, and Monomorine I DOI

Shuangwei Liu,

Xiaojiao Su,

Dan Jiang

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(12), P. 2058 - 2062

Published: March 17, 2023

A Fe(NO3)3-mediated ring-opening arylation of cyclopropanol with the electron-rich pyrrole has been developed, which might proceed through oxidative radical ring opening followed by cyclization to motif and then aromatization. This method enables direct without prefunctionalization thus allows rapid access a diverse array chiral 5,6,7,8-tetrahydroindolizines from easily available amino acid esters. The synthetic utility demonstrated asymmetric synthesis alklaoids (-)-indolizidine 167B, (+)-indolizidine 209D, (+)-monomorine I, natural product analogue.

Language: Английский

Citations

11