4.7 Article

Unprecedented chemoselective Ru(iii)-catalyzed [3+2] annulation of enaminones with iodonium ylides for the synthesis of functionalized 3a,7a-dihydroxy hexahydro-4H-indol-4-ones

Related references

Note: Only part of the references are listed.
Article Chemistry, Applied

Rhodium-Catalyzed Dual C-H Activation for Regioselective Triple Annulation of Enaminones: Access to Polycyclic Naphthopyran Derivatives

Vavilapalli Suresh et al.

Summary: The Rh-catalyzed C-H activation of arenes for oxidative annulations with alkynes is an efficient method to form polycyclic scaffolds. In this study, a regioselective triple annulation of enaminones with hydroxyl-alkynoates via double C-H functionalization was achieved by rhodium catalysis, resulting in polycyclic naphtho-pyran scaffolds. The regioselectivity was controlled by the secondary coordination of hydroxyl group in alkynoate.

ADVANCED SYNTHESIS & CATALYSIS (2023)

Article Chemistry, Multidisciplinary

Organocatalytic Enantioselective Synthesis of Axially Chiral N,N'-Bisindoles

Zhi-Han Chen et al.

Summary: This study introduces a novel strategy for the enantioselective synthesis of axially chiral N,N'-bisindoles using chiral phosphoric acid-catalyzed formal cycloadditions. The synthesized compounds showed excellent yields and enantioselectivities, and exhibited cytotoxicity towards cancer cells. Moreover, they were also transformed into axially chiral phosphine ligands with high catalytic activity.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2023)

Review Chemistry, Multidisciplinary

Transition-Metal-Catalyzed C-H Bond Activation for the Formation of C-C Bonds in Complex Molecules

Jamie H. Docherty et al.

Summary: Site-predictable and chemoselective C-H bond functionalization reactions are synthetically powerful strategies for the diversification of both feedstock and fine chemicals. However, challenges of regio- and chemoselectivity emerge when dealing with complex molecules with significant functional group density and diversity. Design and selection of reaction conditions and tolerant catalysts are critical for successful direct functionalization.

CHEMICAL REVIEWS (2023)

Article Chemistry, Multidisciplinary

Copper-Catalyzed Oxidative [1+2+1+2] Cascade Cyclization of N,N-Dimethyl Enaminones with Benzylamines: A Facile Access to Functionalized 1,4-Dihydropyridines

Yulin Sun et al.

Summary: A Cu-catalyzed oxidative [1+2+1+2] cascade cyclization for the synthesis of 1,4-DHPs was developed using benzylamines as the C4 source. A wide range of N,N-dimethyl enaminones and benzylamines were smoothly employed to provide diverse 1,4-DHPs with high efficiency. This method utilizes a one-pot cascade C(sp(3))-H bond functionalization/C(sp(3))-N cleavage/cyclization strategy to simultaneously form two C(sp(3))-C(sp(2)) bonds, two C(sp(2))-N bonds, and a 1,4-DHP ring.

CHEMISTRY-A EUROPEAN JOURNAL (2023)

Article Chemistry, Organic

Three-Component Fusion to Pyrazolo[5,1-a]isoquinolines via Rh- Catalyzed Multiple Order Transformation of Enaminones

Demao Chen et al.

Summary: A facile and practical method for the synthesis of fused tricyclic pyrazolo[5,1-a]isoquinolines has been developed via the reactions of enaminones, hydrazine hydrochloride, and internal alkynes using Rh catalysis. The cascade reactions demonstrate the remarkable high-order bond functionalization, involving the transformation of aryl C-H, ketone C=O, and alkenyl C-N bonds in the enaminones. This study highlights the individual advantage of enaminones in the design of novel and efficient synthetic methods.

JOURNAL OF ORGANIC CHEMISTRY (2023)

Article Chemistry, Organic

Tunable Key [3+2] and [2+1] Cycloaddition of Enaminones and ?-Diazo Compounds for the Synthesis of Isomeric Isoxazoles: Metal-Controlled Selectivity

Wenli Song et al.

Summary: The switchable synthesis of isomeric isoxazoles has been achieved through three-component reactions of enaminones, alpha-diazo esters/ketones, and t-butyl nitrite (TBN). Catalysis with Cu(II) salt leads to 3,4-disubstituted isoxazoles via [3 + 2] cycloaddition, while catalysis with Ag(I) results in isomeric isoxazoles with reversed C3 and C4 substitution based on a key [2 + 1] cycloaddition.

ORGANIC LETTERS (2023)

Article Chemistry, Organic

Catalytic Olefin-Imine Metathesis: Cobalt-Enabled Amidine Olefination with Enaminones

Shuaixin Fan et al.

Summary: Organic metathesis reactions can efficiently assemble diverse molecular skeletons and appendages through the exchange of molecular fragments. A catalytic olefin-imine metathesis reaction, featuring cobalt-catalyzed amidine olefination, has been developed, providing a versatile toolbox for manipulating carbon-carbon and carbon-nitrogen bonds.

ORGANIC LETTERS (2023)

Article Chemistry, Organic

Hydroxyl-Directed Rh(III)-Catalyzed C-H Functionalization: Access to Benzo[de]chromenes

Xing-Mei Hu et al.

Summary: A cascade oxidative annulation reaction of heterocyclic ketene aminals (HKAs) with internal alkynes catalyzed by [Cp*RhCl2]2 and oxidized by Cu(OAc)2·H2O was developed for the efficient synthesis of highly functionalized benzo[de]chromene derivatives in good to excellent yields. The reaction proceeded through sequential cleavage of C(sp2)-H/O-H and C(sp2)-H/C(sp2)-H bonds, and exhibited high regioselectivity. Additionally, the resulting benzo[de]chromene products showed intense fluorescence emission in the solid state and concentration-dependent quenching in the presence of Fe3+, indicating their potential for Fe3+ recognition.

ORGANIC LETTERS (2023)

Article Chemistry, Applied

Synthesis of Substituted 1-Hydroxy-2-Naphthaldehydes by Rhodium-Catalyzed C-H Bond Activation and Vinylene Transfer of Enaminones with Vinylene Carbonate

Min Liu et al.

Summary: A method using rhodium(III) catalysis for the synthesis of substituted 1-hydroxy-2-naphthaldehydes through the reaction of enaminones with vinylene carbonate has been proposed, providing an alternative approach for the synthesis of these compounds with yields ranging from 49-84%. Preliminary mechanistic studies and hydroxyl-directed derivatization reactions of 1-hydroxy-2-naphthaldehydes were also conducted.

ADVANCED SYNTHESIS & CATALYSIS (2022)

Review Chemistry, Multidisciplinary

Toolbox for Distal C-H Bond Functionalizations in Organic Molecules

Soumya Kumar Sinha et al.

Summary: Transition-metal-catalyzed C-H activation is a contemporary synthetic approach that has significant impact and importance in the synthesis of natural products and pharmaceutical drugs.

CHEMICAL REVIEWS (2022)

Article Chemistry, Organic

Rhodium-Catalyzed Regioselective Double Annulation of Enaminones with Propargyl Alcohols: Rapid Access to Arylnapthalene Lignan Derivatives

Attunuri Nagireddy et al.

Summary: This research presents a rhodium-catalyzed oxidative three-point double annulation of enaminones with propargylic alcohols to access arylnaphthalene-based lignan derivatives. The key step involves the regioselective insertion of propargylic alcohol into the rhoda-cycle due to hydroxyl rhodium coordination, with mechanism determined through control experiments and KIE studies.

JOURNAL OF ORGANIC CHEMISTRY (2022)

Article Chemistry, Organic

Rh-Catalyzed [4+2] Annulation with a Removable Monodentate Structure toward Iminopyranes and Pyranones by C-H Annulation

Leiqing Fu et al.

Summary: The Rh-catalyzed reactions of N-pyridinyl enaminones with internal alkynes leading to the synthesis of iminopyranes via C-H bond activation and subsequent tautomeric O-H bond cleavage are reported. The pyridine ring in the amino group acts as an auxiliary monodentate site and can be easily removed by hydrolysis to afford pyranones.

ORGANIC LETTERS (2022)

Article Chemistry, Organic

Ru(II)-Catalyzed Decarbonylative Alkylation and Annulations of Benzaldehydes with Iodonium Ylides under Chelation Assistance

Xiang Li et al.

Summary: A Ru(II)-catalyzed synthesis method has been developed for the efficient formation of dibenzo[b,d]furans and NH-free carbazolones. The reaction shows mild conditions, low catalyst loading, and broad substrate compatibility. Hydroxy and free amino groups were found to be effective directing groups.

ORGANIC LETTERS (2022)

Review Chemistry, Multidisciplinary

Recent Advances in Alkenyl sp2 C-H and C-F Bond Functionalizations: Scope, Mechanism, and Applications

Ming-Zhu Lu et al.

Summary: This comprehensive review provides an overview of the latest methods for selectively activating alkenyl C(sp2)-H and C-F bonds to access alkenes and their derivatives. It is divided into two parts, the first part focuses on C-H functionalization methods using different alkene derivatives as starting materials, and the second part describes C-F bond functionalization using easily accessible gem-difluoroalkenes. The review includes scope, limitations, mechanistic studies, stereoselective control, and applications in complex molecule synthesis.

CHEMICAL REVIEWS (2022)

Article Chemistry, Organic

Rhodium(III)-Catalyzed Triple Aryl/Alkenyl C-H Bond Activation of Aryl Enaminones to Access Naphtho[1,8-bc]pyrans

Yunlong Li et al.

Summary: In this study, triple C-H bond activation of aryl enaminones was achieved to access naphtho[1,8-bc]pyrans through oxidative annulation. Depending on the steric and/or electronic environment around the aryl moiety of the enaminones or the electronic impact from the alkynes, 1-naphthols might be formed as the sole products. By using propargyl alcohols as masked terminal alkynes, functionalized but-2-ene-1,4-diones were obtained through rhodium(III)- or rhodium(I)-catalyzed internal alkenyl C-H bond activation. The resulting naphtho[1,8-bc]pyrans exhibited high fluorescence and could be further transformed by chlorination, bromination, and difluoromethylation, demonstrating the potential applicability of the synthetic protocol.

ORGANIC LETTERS (2022)

Article Chemistry, Organic

Rh(III)-Catalyzed Enaminone-Directed C-H Coupling with Diazodicarbonyls for Skeleton-Divergent Synthesis of Isocoumarins and Naphthalenes

Weiping Wu et al.

Summary: Diversity-oriented synthesis is a valuable method for expanding the chemical space, but its application is limited by the available toolbox for skeleton-diversification chemistry. In this study, we report the Rh(III)-catalyzed coupling of enaminones and diazodicarbonyls for the synthesis of isocoumarins and naphthalenes with divergent skeletons. The dependence of the skeleton-forming process on the ring size of diazodicarbonyls and pH demonstrates the achievement of both substrate-and reagent-controlled skeletal diversity generation in a single system. Moreover, the C-C bond cleavage reactivity is found to be critical for facile synthetic access to isocoumarins.

ORGANIC LETTERS (2022)

Article Chemistry, Multidisciplinary

Rh(iii)-catalyzed C-H/C-C bond annulation of enaminones with iodonium ylides to form isocoumarins

Zi Yang et al.

Summary: A straightforward approach to synthesise isocoumarins via Rh(iii)-catalyzed C-H/C-C bond activation/annulation cascade of enaminones and iodonium ylides has been explored. The established protocol is characterized by an exceedingly simple reaction system, high regioselectivity and good functional group tolerance. Moreover, this strategy may provide a new route to cleavage of the C(sp(2))-C(O) bond of unstrained ketones.

CHEMICAL COMMUNICATIONS (2022)

Article Chemistry, Organic

I2-Promoted site-selective C-C bond cleavage of aryl methyl ketones as C1 synthons for constructing 5-acyl-1H-pyrazolo[3,4-b]pyridines

You Zhou et al.

Summary: A novel iodine promoted reaction was developed for the synthesis of 1H-pyrazolo[3,4-b]pyridines. This transition metal-free catalysis method has simple reaction conditions and good substrate compatibility and has been demonstrated in the transformation of various enaminones. Mechanistic studies revealed involvement of two different cyclization pathways leading to the same target product through selective cleavage of the acyl group.

ORGANIC CHEMISTRY FRONTIERS (2022)

Article Chemistry, Organic

Facile approach to multifunctionalized 5-alkylidene-3-pyrrolin-2-ones via regioselective oxidative cyclization of 2,4-pentanediones with primary amines and sodium sulfinates

Donghan Liu et al.

Summary: A cascade cyclization reaction of multi-component was reported, which can efficiently synthesize highly functionalized compounds. The reaction was conducted under mild conditions and showed good yields.

ORGANIC CHEMISTRY FRONTIERS (2022)

Review Chemistry, Multidisciplinary

Transition-Metal-Catalyzed, Coordination-Assisted Functionalization of Nonactivated C(sp3)-H Bonds

Bin Liu et al.

Summary: Transition-metal-catalyzed, coordination-assisted C(sp(3))-H functionalization has revolutionized synthetic planning by providing increased access to strategic positions in organic molecules. Challenges like high temperatures, difficulty in removing directing groups, and limited metal options beyond palladium still remain. This review aims to cover literature since 2004, highlighting current state-of-the-art methods, limitations, and discussing synthetic applications and reaction mechanisms.

CHEMICAL REVIEWS (2021)

Article Chemistry, Organic

Preparation of Thiazole-2-thiones through TBPB-Promoted Oxidative Cascade Cyclization of Enaminones with Elemental Sulfur

Biao Zhang et al.

Summary: An unprecedented method for constructing thiazole-2-thiones via an oxidative cascade cyclization strategy is described, allowing for the efficient synthesis of thiazole-2-thiones with broad tolerance.

ORGANIC LETTERS (2021)

Article Chemistry, Medicinal

Development of Alectinib-Based PROTACs as Novel Potent Degraders of Anaplastic Lymphoma Kinase (ALK)

Shaowen Xie et al.

Summary: Novel ALK degraders based on PROTAC technology showed high specificity in ALK-positive cell lines and significant anti-tumor effects in a mouse model, indicating potential benefits for treating ALK-driven malignancies.

JOURNAL OF MEDICINAL CHEMISTRY (2021)

Article Chemistry, Organic

Catalytic Acceptorless Dehydrogenation of Amino Alcohols and 2-Hydroxybenzyl Alcohols for Annulation Reaction under Neutral Conditions

Akanksha M. Pandey et al.

Summary: A base-free and acceptorless Ru-catalyzed dehydrogenative approach has been developed for the synthesis of N-heterocycles and O-heterocycles, which is applicable for the preparation of biologically important scaffolds.

JOURNAL OF ORGANIC CHEMISTRY (2021)

Article Chemistry, Organic

Rh(III)-Catalyzed [5+1] Annulation of Indole-enaminones with Diazo Compounds To Form Highly Functionalized Carbazoles

Zhidong Jiang et al.

Summary: A novel Rh(III)-catalyzed C-H activation/annulation cascade of indole-enaminones with diazo compounds was reported, generating diversely functionalized carbazole frameworks with good to excellent yields. The most notable feature is the formation of a novel [5 + 1] cyclization product, accompanied by the complete removal of acetyl and N,N-dimethyl groups from the substrates, rather than the expected [4 + 2] cyclization products.

ORGANIC LETTERS (2021)

Article Multidisciplinary Sciences

Diversity-oriented functionalization of 2-pyridones and uracils

Yong Shang et al.

Summary: The derivatives of heterocycles 2-pyridone and uracil are important pharmacophores in medicinal chemistry, and there is an urgent need for diverse synthesis of such derivatives. This study demonstrates that palladium/norbornene cooperative catalysis enables dual-functionalization of iodinated 2-pyridones and uracils.

NATURE COMMUNICATIONS (2021)

Article Chemistry, Physical

Palladium-Catalyzed meta-Selective C-H Functionalization by Noncovalent H-Bonding Interaction

Guoshuai Li et al.

Summary: A new palladium-catalyzed meta-selective C-H olefination of aromatic carbonyl compounds was achieved by utilizing noncovalent hydrogen-bonding interaction directed by engineered N,N'-substituted ureas, demonstrating site-selective control without the need for prior stoichiometric installation and removal of directing groups.

ACS CATALYSIS (2021)

Article Chemistry, Physical

Rh-Catalyzed Cascade C-C/Colefin-H Activations and Mechanistic Insight

Yuxi Wang et al.

Summary: The reverse concerted metalation-deprotonation (CMD) process is proposed as a key step in rationalizing a newly discovered Rh-catalyzed C-C/olefin-H cascade reaction, which features redox-neutral conditions with 100% atom economy, broad substrate scope, and high efficiency (23 examples, up to 85% yield). DFT calculations suggest that the reverse CMD process is crucial in kinetic override of the normal cut and sew process, leading to the activation of olefinic C-H bonds as the predominant pathway.

ACS CATALYSIS (2021)

Article Chemistry, Applied

Electrochemical Dearomative Dihydroxylation and Hydroxycyclization of Indoles

Ju Wu et al.

ADVANCED SYNTHESIS & CATALYSIS (2020)

Review Chemistry, Physical

Transition Metal Catalyzed Enantioselective C(sp2)-H Bond Functionalization

Tapas Kumar Achar et al.

ACS CATALYSIS (2020)

Article Chemistry, Multidisciplinary

Electrochemical Dearomative 2,3-Difunctionalization of Indoles

Ju Wu et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2019)

Article Chemistry, Multidisciplinary

Unified biomimetic assembly of voacalgine A and bipleiophylline via divergent oxidative couplings

David Lachkar et al.

NATURE CHEMISTRY (2017)

Article Chemistry, Multidisciplinary

Enaminones as Synthons for a Directed C-H Functionalization: RhIII-Catalyzed Synthesis of Naphthalenes

Shuguang Zhou et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2016)

Article Chemistry, Multidisciplinary

Zinc-Catalyzed Alkyne Oxidation/CH Functionalization: Highly Site-Selective Synthesis of Versatile Isoquinolones and -Carbolines

Long Li et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2015)

Article Chemistry, Multidisciplinary

Rh-Catalyzed Construction of Quinolin-2(1H)-ones via C-H Bond Activation of Simple Anilines with CO and Alkynes

Xinyao Li et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2015)

Article Chemistry, Organic

One-pot synthesis of polysubstituted 3-acylpyrroles by cooperative catalysis

Hai-Lei Cui et al.

ORGANIC & BIOMOLECULAR CHEMISTRY (2014)

Review Chemistry, Multidisciplinary

Mitomycinoid Alkaloids: Mechanism of Action, Biosynthesis, Total Syntheses, and Synthetic Approaches

Phillip D. Bass et al.

CHEMICAL REVIEWS (2013)

Article Chemistry, Medicinal

Discovery of novel aminoquinazolin-7-yl 6,7-dihydro-indol-4-ones as potent, selective inhibitors of heat shock protein 90

Kenneth H. Huang et al.

BIOORGANIC & MEDICINAL CHEMISTRY LETTERS (2012)

Article Chemistry, Medicinal

Discovery of Pyrrole-Indoline-2-ones as Aurora Kinase Inhibitors with a Different Inhibition Profile

Chao-Cheng Chiang et al.

JOURNAL OF MEDICINAL CHEMISTRY (2010)

Review Chemistry, Multidisciplinary

Transition metal-catalyzed C-H activation reactions: diastereoselectivity and enantioselectivity

Ramesh Giri et al.

CHEMICAL SOCIETY REVIEWS (2009)

Article Chemistry, Multidisciplinary

Synthesis of 3-alkylidene-1,2,3,5,6,7-hexahydro-4H-indol-4-one derivatives in the THF-H2O system

I Yavari et al.

MENDELEEV COMMUNICATIONS (2005)