Asymmetric Hydroxymethylative Etherification of 1,3-Dienes with Isatins and Alcohols via Pd(0)-π-Lewis Base Catalysis DOI

Bo Jiang,

Haotian Wang, Zhichao Chen

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 14(2), P. 628 - 636

Published: Dec. 28, 2023

Although the asymmetric hydroalkoxylation of 1,3-dienes has been achieved recently, development a modular and mechanistically distinct strategy for concurrently introducing an alkoxyl group another chiral moiety into remains to be disclosed. Presented herein is palladium(0)-π-Lewis base-catalyzed hydroxymethylative etherification reaction 1,3-dienes, isatins, aliphatic alcohols, proceeding through cascade vinylogous addition allylic sequence. This three-component exhibits broad substrate scope good functionality tolerance under mild catalytic conditions, generally furnishing structurally diverse 1,3-diol derivatives bearing two stereogenic centers with moderate-to-high levels diastereo- enantioselectivity, which can further converted valuable frameworks higher molecular complexity. In addition, few control experiments were conducted elucidate process.

Language: Английский

Pd-Catalyzed Hydrocyanation of Methylenecyclopropanes: A Highly Selective Ring-Opening Access to 2-Substituted Allylic Nitriles DOI

Mingdong Jiao,

Haijun Fang,

Jianxi Chen

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(44), P. 9431 - 9435

Published: Oct. 30, 2024

Transition-metal-catalyzed hydrofunctionalization of methylenecyclopropanes presents a useful but challenging transformation due to the complex selectivity and multiple reaction pathways. We describe herein an unprecedented highly efficient selective palladium-catalyzed hydrocyanation give various 2-substituted allylic nitriles. Mechanistic studies demonstrated that may undergo Markovnikov-type hydrometalation β-carbon elimination.

Language: Английский

Citations

2
Molecular Diversity of Base Promoted Annulation of MBH Carbonates of Isatins and Dialkyl But‐2‐ynedioates DOI Open Access
Ting Tang, Xueyan Liu,

Jing Sun

et al.

ChemistrySelect, Journal Year: 2023, Volume and Issue: 8(39)

Published: Oct. 19, 2023

Abstract DABCO promoted one‐pot three‐component reaction of aromatic amines, dialkyl but‐2‐ynedioates and MBH nitriles isatins selectively afforded two diastereomeric spiro[indoline‐3,4′‐pyridines] in comparable yields. On the other hand, cyclization carbonates DCM at room temperature gave spiro[cyclopentane‐1,3′‐indoline] derivatives, while chloroform 70 °C resulted unique cyclopenta[ c ]quinolone derivatives with ring‐opening isatin moiety. A plausible mechanism was rationally proposed to explain formation different products.

Language: Английский

Citations

4
Recent Advances in Asymmetric Addition Reactions to Isatins DOI
Ke Xie, Ao Li, Zhichao Chen

et al.

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

Published: July 30, 2024

Abstract The 3-substituted-3-hydroxy-2-oxindole scaffolds are not only widely encountered in bioactive compounds but also serve as versatile building blocks for the construction of diverse valuable architectures. Although numerous synthetic methodologies have been developed over past decades, asymmetric addition nucleophiles or their equivalents to isatin substrates has proved be one most efficient strategies synthesis chiral 3-substituted-3-hydroxy-2-oxindoles. This Short Review aims summarize significant progress achieved this field recent years, with particular attention paid reaction development, mechanism, and stereo-induction models. 1 Introduction 2 Asymmetric Alkylation Isatins 3 Alkenylation Dienylation 4 Alkynylation 5 Allenylation 6 Arylation 7 Annulations 8 Conclusions Outlooks

Language: Английский

Citations

1
Harnessing Dpp-Imine as a Powerful Achiral Cocatalyst to Dramatically Increase the Efficiency and Stereoselectivity in a Magnesium-Mediated Oxa-Michael Reaction DOI Creative Commons

Yingfan Xu,

Dan Liu,

Feiyun Gao

et al.

JACS Au, Journal Year: 2023, Volume and Issue: 4(1), P. 164 - 176

Published: Dec. 21, 2023

Dpp-imines are classic model substrates for synthetic method studies. Here, we disclose their powerful use as achiral coligands in metal-catalyzed reactions. It is highly interesting to find that the Dpp-imine can not only act ligand create excellent chiral pockets with magnesium complexes but also, more importantly, this coligand dramatically enhance catalytic ability of metal catalyst. The underlying reaction mechanism was extensively explored by conducting a series experiments, including

Language: Английский

Citations

3
Phosphine-Promoted Tandem Intermolecular Diels–Alder Reactions with Pentadienyl 4-Nitrobenzoate as a Diene Precursor DOI
Le Zhang, Ye Liu,

Chao-Xu Li

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(35), P. 6506 - 6510

Published: Aug. 25, 2023

A phosphine-promoted tandem Diels–Alder reaction using pentadienyl 4-nitrobenzoate (α-vinyl MBH adduct) as a diene precursor with 3-olefinic oxindoles or CF3-activated ketones dienophiles has been developed. The proceeds through the formation of phosphonium intermediate via SN2′′ addition, which acts both D–A and for exomethylene moiety. This method offers metal-free step-efficient approach synthesizing exomethylene-bearing spirooxindoles dihydropyrans, are privileged structures found in natural products.

Language: Английский

Citations

2
Synthesis of Quinolinoneylnitrones and Coumarinylnitrones via a Cascade Hydroamination and Aza-MBH-Type Reaction DOI
Yan Zhang, Qingtao Wang,

Zhiwu Long

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(14), P. 10327 - 10332

Published: July 4, 2024

Nitrones are quite useful intermediates and have been broadly applied in organic synthesis, drug discovery, photochemistry research. Many functional nitrones successfully prepared using various strategies. In this work, an efficient method for synthesizing novel quinolinoneylnitrone coumarinylnitrone derivatives was developed. Preliminary mechanistic research suggests that protocol included a cascade hydroamination aza-MBH-type reaction.

Language: Английский

Citations

0
Palladium(0) and Brønsted Acid Co‐catalyzed Enantioselective Hydro‐Cyclization of 2,4‐Dienyl Hydrazones and Oximes DOI
Yufan Li,

Wu-Tao Gui,

Fu Pi

et al.

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

Published: Aug. 6, 2024

Abstract The transition metal‐catalyzed asymmetric hydro‐functionalization of 1,3‐dienes has been well explored, but most reactions focus on electron‐neutral substrates in an intermolecular manner. Here we first demonstrate that readily available 2,4‐dienyl hydrazones and oximes can be efficiently utilized the hydro‐cyclization reaction under co‐catalysis a Brønsted acid chiral palladium complex, furnishing multifunctional dihydropyrazones dihydroisoxazoles, respectively. Diverse substitution patterns for both types electron‐deficient diene compounds are tolerated, corresponding heterocycles were generally constructed with moderate to excellent enantioselectivity, which elaborated access products higher molecular complexity diversity. Control experiments density functional theory calculations support α‐regioselective protonation dienyl by concurrent π‐Lewis base activation Pd 0 complex is energetically favoured formation active π‐allylpalladium intermediates, outer‐sphere allylic amination or etherification mode adopted deliver observed cyclized enantioselectively.

Language: Английский

Citations

0
Asymmetric Hydroxymethylative Etherification of 1,3-Dienes with Isatins and Alcohols via Pd(0)-π-Lewis Base Catalysis DOI

Bo Jiang,

Haotian Wang, Zhichao Chen

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 14(2), P. 628 - 636

Published: Dec. 28, 2023

Although the asymmetric hydroalkoxylation of 1,3-dienes has been achieved recently, development a modular and mechanistically distinct strategy for concurrently introducing an alkoxyl group another chiral moiety into remains to be disclosed. Presented herein is palladium(0)-π-Lewis base-catalyzed hydroxymethylative etherification reaction 1,3-dienes, isatins, aliphatic alcohols, proceeding through cascade vinylogous addition allylic sequence. This three-component exhibits broad substrate scope good functionality tolerance under mild catalytic conditions, generally furnishing structurally diverse 1,3-diol derivatives bearing two stereogenic centers with moderate-to-high levels diastereo- enantioselectivity, which can further converted valuable frameworks higher molecular complexity. In addition, few control experiments were conducted elucidate process.

Language: Английский

Citations

1