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1.
Angew Chem Int Ed Engl ; : e202404275, 2024 Apr 30.
Artigo em Inglês | MEDLINE | ID: mdl-38687058

RESUMO

Herein, we present a radical cascade addition cyclization sequence to access quinoline-based benzophosphole oxides from ortho-alkynylated aromatic phosphine oxides using various aryl isonitriles as radical acceptors and inexpensive tert-butyl-hydroperoxide (TBHP) as a terminal oxidant in the presence of a catalytic amount of silver acetate. Alternatively, the same cascade can be realized through a sustainable photochemical approach utilizing 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) as an organic photocatalyst at room temperature. The introduced modular approach shows broad functional group tolerance and offers straightforward access to complex P,N-containing polyheterocyclic arenes. These novel π-extended benzophosphole oxides exhibit interesting photophysical and electrochemical properties such as absorption in the visible region, emission and reversible reduction at low potentials, which makes them promising for potential materials science applications. The photophysical properties can further be tuned by addition of external Lewis and Brønsted acids.

2.
Org Lett ; 26(10): 2091-2096, 2024 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-38441887

RESUMO

Herein, we report the facile synthesis of indole C(4)-acrylophenone using a C-H bond activation strategy. For this conversion, an unsymmetrical alkyne (phenylethynyl ether) in the presence of cobalt(III)-catalyst works efficiently. In this process, alkyne gets oxidized in the presence of in situ generated water, which is the key step for this method, for which trifluoroethanol is the water source. The pivaloyl directing group chelates effectively to generate the cobaltacycle intermediate, which was detected through high-resolution mass spectrometry (HRMS). Also, the formation of bis(2,2,2-trifluoroethyl) ether has been confirmed and quantified using 19F NMR. In addition, the applicability of obtained indole C(4)-acrylophenone product has been demonstrated by performing the Nazarov cyclization and conjugate addition to the α,ß-unsaturated ketone moiety.

3.
Dalton Trans ; 52(44): 16151-16158, 2023 Nov 14.
Artigo em Inglês | MEDLINE | ID: mdl-37603440

RESUMO

Two novel dicationic binuclear Cu(I) complexes of the type [{(BPPP)E2}Cu]2[BF4]2 (E = S (3a); Se (3b)) bearing (BPPP)E2 (BPPP = bis(diphenylphosphino)pyridine) pincer systems were isolated, and structurally characterized. The solid-state structures of 3a/3b display the presence of intermolecular cuprophilic (Cu⋯Cu) interactions between the two monocationic species, and consist of weak Cu⋯S bonding between the two cations. Besides, complex 3a was introduced as a molecular copper(I) catalyst in cyclization reactions, and new protocols were developed for the synthesis of a series of new oxazole and triazole derivatives bearing alkyne-phenyl propargylic ether substituents. 3a was also found to be active in achieving these two classes of heterocyclic compounds by the mechanical grinding method. One of the key intermediate copper-azide species was detected by the high-resolution mass spectrometry technique, which supports the proposed catalytic pathway. All the reported transformations were accomplished sustainably by employing a well-defined, earth-abundant, and cheap copper(I) catalytic system.

4.
Org Lett ; 25(34): 6424-6428, 2023 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-37610878

RESUMO

An oxidative radical cascade addition cyclization approach for the synthesis of quinoline-based π-extended polyheterocyclic compounds is reported. Eco-friendly iron catalysis and inexpensive tert-butylhydroperoxide (TBHP) as the oxidant have been utilized in the transformation of various readily available ortho-alkynylated aromatic aldehydes as radical precursors with aryl isonitriles as radical acceptors. Indole and thiophene-based carbaldehydes allow the preparation of quinolines that are π-conjugated with an additional heteroarene moiety in a single sequence by applying the introduced method.

5.
Org Biomol Chem ; 21(14): 2842-2869, 2023 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-36917476

RESUMO

This review provides a broad overview of the recent developments in the field of transition metal-catalyzed C-H/C-C bond activation and coupling with 1,3-diyne for assembling alkynylated heterocycles, bis-heterocycles, and 1,3-enynes. Transition metal-catalyzed inert bond (C-H/C-C) activation has been the focus of attention among synthetic chemists in recent times. Enormous developments have taken place in C-H/C-C bond activation chemistry in the last two decades. In recent years the use of 2π-unsaturated units as coupling partners for the synthesis of heterocycles through C-H/C-C bond activation and annulation sequence has received immense attention. Among the unsaturated units employed for assembling heterocycles, the use of 1,3-diynes has garnered significant attention due to its ability to render bis-heterocycles in a straightforward manner. The C-H bond activation and coupling with 1,3-diyne has been very much explored in recent years. However, the development of strategies for the use of 1,3-diynes in the analogous C-C bond activation chemistry is less explored. Earlier methods employed to assemble bis-heterocycle used heterocycles that were preformed and pre-functionalized via transition metal-catalyzed coupling reactions. The expensive pre-functionalized halo-heterocycles and sensitive and expensive heterocyclic metal reagents limit its broad application. However, the transition metal-catalyzed C-H activation obviates the need for expensive heterocyclic metal reagents and pre-functionalized halo-heterocycles. The C-H bond activation strategy makes use of C-H bonds as functional groups for effecting the transformation. This renders the overall synthetic sequence both step and cost economic. Hence, this strategy of C-H activation and subsequent reaction with 1,3-diyne could be used for the larger-scale synthesis of chemicals in the pharmaceutical industry. Despite these advances, there is still the possibility of exploration of earth-abundant and cost-effective first-row transition metals (Ni, Cu, Mn. Fe, etc.) for the synthesis of bis-heterocycles. Moreover, the Cp*-ligand-free, simple metal-salt-mediated synthesis of bis-heterocycles is also less explored. Thus, more exploration of reaction conditions for the Cp*-free synthesis of bis-heterocycles is called for. We hope this review will inspire scientists to investigate these unexplored domains.

6.
J Org Chem ; 88(2): 952-959, 2023 Jan 20.
Artigo em Inglês | MEDLINE | ID: mdl-36606375

RESUMO

Herein, we report the annulation of indole-2-carboxamides with bicycloalkenes, to synthesize ß-carboline-1-one derivatives under mild conditions. The commercially available ruthenium catalyst was used for the reaction. This reaction tolerates a wide range of functional groups and affords a good yield of ß-carboline-1-one derivatives. A reversible cyclometalation pathway was found to be operative in the mechanistic study.

7.
Org Lett ; 25(1): 251-255, 2023 Jan 13.
Artigo em Inglês | MEDLINE | ID: mdl-36580352

RESUMO

The sustainable C-H bond ethynylation of N-aryl γ-lactam has been achieved in a highly regioselective manner. In this protocol, earth-abundant cobalt(III)-catalyst was found to be effective, triggering the C-H metalation using a weakly coordinating lactam group. Herein, the ortho-(sp2)-H ethynylation has been obtained regioselectively. The mechanistic studies reveal the non-involvement of the radical pathway for this conversion. However, the parallel kinetic isotope experiment suggests that the C-H bond activation is involved in the rate-determining step. In addition, the synthetic utility of ethynylated N-aryl γ-lactam has been demonstrated for many useful transformations.

8.
Chem Commun (Camb) ; 59(2): 199-202, 2022 Dec 22.
Artigo em Inglês | MEDLINE | ID: mdl-36476727

RESUMO

A Rh-catalyzed C(sp2)-H propenylation has been reported by taking N-allyl benzimidazole as an allylamine congener. This transformation has been observed for the first time, where a tandem process of C-H allylation followed by alkene isomerization delivers a highly stereoselective trans-propenylated product. Detailed mechanistic studies including the characterization of rhodacycle-intermediates have been conducted to understand the mechanism.


Assuntos
Alilamina , Ródio , Ródio/química , Catálise , Alcenos/química
9.
Chem Commun (Camb) ; 58(74): 10262-10289, 2022 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-36040423

RESUMO

Alkynes occupy a prominent role as a coupling partner in the transition metal-catalysed directed C-H activation reactions. Due to low steric requirements and linear geometry, alkynes can effectively coordinate with metal d-orbitals. This makes alkynes one of the most successful coupling partners in terms of the number of useful transformations. Remarkably, by changing the reaction conditions and transition-metals from 5d to 3d, the pattern of reactivity of alkynes also changes. Due to the varied reactivity of alkynes, such as alkenylation, annulation, alkylation, and alkynylation, they have been extensively used for the synthesis of valuable organic molecules. Despite enormous explorations with alkynes, there are still a lot more possible ways by which they can be made to react with M-C bonds generated through C-H activation. Practically there is no limit for the creative use of this approach. In particular with the development of new high and low valent first-row metal catalysts, there is plenty of scope for this chemistry to evolve as one of the most explored areas of research in the coming years. Therefore, a highlight article about alkynes is both timely and useful for synthetic chemists working in this area. Herein, we have highlighted the diverse reactivity of alkynes with various transition metals (Ir, Rh, Ru, Pd, Mn, Fe, Co, Ni, Cu) and their applications, along with some of our thoughts on future prospects.

10.
Org Lett ; 24(33): 6122-6127, 2022 Aug 26.
Artigo em Inglês | MEDLINE | ID: mdl-35952663

RESUMO

A Ni-catalyzed C6 followed by C5 cascade C-H activation/[2 + 2 + 2] annulation of 2-pyridone with alkynes has been achieved. A change in the reaction pathway was achieved by tuning the reaction conditions and incorporating a directing group. A wide variety of substrates and alkynes are amenable to this transformation. The key to success for this transformation is the use of sodium iodide as an additive. More importantly, we detected the five-membered metallacycle intermediate through HRMS wherein iodide is ligated to the metal.

11.
Org Lett ; 24(31): 5651-5656, 2022 Aug 12.
Artigo em Inglês | MEDLINE | ID: mdl-35920685

RESUMO

We report here a Rh(III) catalyzed regio- and stereoselective synthesis of alkynylated and bis-isocoumarin from 1,3-dialkyne. Exclusive one-pot formation of 3,3-bis-isocoumarin isomers has been achieved by eliminating several other possibilities. This is the first example of transition metal catalyzed synthesis of alkynylated and bis-isocoumarin scaffolds. The protocol is compatible with a wide range of functional groups affording good to excellent yields. Several mechanistic investigations, including deuterium labeling experiments and kinetic isotope effect studies, have been carried out.

12.
J Org Chem ; 87(9): 6189-6201, 2022 05 06.
Artigo em Inglês | MEDLINE | ID: mdl-35467333

RESUMO

Herein, the ruthenium-catalyzed regioselective sp2(C-H) monoalkenylation of N-arylpyridones has been demonstrated, where the pyridone was utilized as a weakly coordinating directing group. Importantly, the current methodology has been effectively applied to the synthesis of many drug analogues such as pirfenidone, naproxen, ibuprofen, geraniol, umbelliferone, pregnenolone, and estrone. This methodology tolerates a wide range of functional groups and yields up to 93% yield. A six-membered ruthenium complex was also detected by HRMS.


Assuntos
Compostos Heterocíclicos , Rutênio , Catálise , Piridonas , Rutênio/química
13.
Chem Sci ; 13(9): 2692-2700, 2022 Mar 02.
Artigo em Inglês | MEDLINE | ID: mdl-35340856

RESUMO

The stereoselective synthesis of 1,3-enynes from 1,3-diynes is demonstrated by palladium-catalyzed selective C-C bond cleavage of cyclopropanol. Exclusive formation of mono-alkenylated adducts was achieved by eliminating the possibility of di-functionalization with high stereoselectivity. Indeed, this protocol worked very well with electronically and sterically diverse substrates. Several studies, including deuterium labeling experiments and intermolecular competitive experiments, were carried out to understand the mechanistic details. The atomic-level mechanism followed in the catalytic process was also validated using DFT calculations, and the rate-controlling states in the catalytic cycle were identified. Furthermore, preliminary mechanistic investigations with radical scavengers revealed the non-involvement of the radical pathway in this transformation.

14.
J Org Chem ; 87(6): 4438-4448, 2022 Mar 18.
Artigo em Inglês | MEDLINE | ID: mdl-35226810

RESUMO

We report herein a cobalt-catalyzed 8-aminoquinoline-directed highly regio- and stereoselective C-H/N-H activation annulation of indole-2-carboxamides with 1,2-dihydronaphthalene for the synthesis of ß-carboline-1-one derivatives at room temperature. A cheaper and commercially available cobalt catalyst has been used for this transformation. The protocol tolerates a wide range of functionalities, affording ß-carboline-1-one derivatives in good yields. An initial mechanistic study revealed a reversible cyclometalation to be operative.

15.
Org Lett ; 24(3): 848-852, 2022 Jan 28.
Artigo em Inglês | MEDLINE | ID: mdl-35040656

RESUMO

An earth-abundant and inexpensive Mn(I)-catalyzed alkylation of 2-pyridone with maleimide has been reported for the first time, in contrast to previously reported Diels-Alder products. Notably, an unexpected rearrangement has been discovered in the presence of acetic acid, which also provides a unique class of compounds bearing three different N-heterocycles with an all-carbon quaternary center. Furthermore, single crystal X-ray and HRMS revealed a five-membered manganacycle intermediate. This methodology tolerates a wide variety of functional groups delivering the alkylated products in moderate to excellent yields.

16.
Org Lett ; 23(23): 9041-9046, 2021 Dec 03.
Artigo em Inglês | MEDLINE | ID: mdl-34788053

RESUMO

Herein, nickel-catalyzed synthesis of polyarylcarbazole through sequential C-H bond activations has been described. Regioselective indole C2/C3 functionalization has been achieved in the presence of indole C7-H, which is quite challenging. In addition, this approach also gives easy access to building a heteropolycyclic motif through C6/C7 C-H functionalization of indoline. This methodology is not limited to aromatic internal alkynes as coupling partners; aliphatic alkynes have also shown good tolerance. Notably, during the optimization the catalytic enhancement with sodium iodide as an additive has been observed. We have also studied the photophysical properties of these highly conjugated molecules.

17.
Chem Commun (Camb) ; 57(30): 3630-3647, 2021 Apr 18.
Artigo em Inglês | MEDLINE | ID: mdl-33870349

RESUMO

This review focuses on providing comprehensive highlights of the recent advances in the field of cobalt-catalysed C-H functionalization and related synthetic concepts, relying on these through oxygen atom coordination. In recent years, 3d transition metal (Fe, Co, Cu & Ni) catalysed C-H functionalization reactions have received immense attention on account of its higher abundance and low cost, as compared to noble metals such as Ir, Rh, Ru and Pd. Among the first-row transition metals, cobalt is one of the extensively used metals for sustainable synthesis due to its unique reactivity towards the functionalization of inert C-H bonds. The functionalization of the inert C-H bond necessitates a proximal directing group. In this context, strongly coordinating nitrogen atom directed C-H functionalizations have been well explored. Nevertheless, strongly coordinating nitrogen-containing scaffolds, such as pyridine, pyrimidine, and 8-aminoquinoline, have to be installed and removed in a separate process. In contrast, C-H functionalizations through weakly coordinating atoms, such as oxygen, are largely underdeveloped. Since the oxygen atom is a part of many readily available functional groups, such as aldehydes, ketones, carboxylic acids, and esters, it could be used as directing groups for selective C-H functionalization reactions without any modification. Thus, the use of 3d transition metals, such as cobalt, along with weakly coordinating (oxygen) directing groups for C-H functionalization reactions are more sustainable, especially for the large-scale production of pharmaceuticals in industries. During the last decade, notable progress has been made using this concept. Nonetheless, almost all the reports are restricted to the formation of C-C and C-N bond. Therefore, there is a wide scope for developing this area for the formation of other bonds, such as C-X (halogens), C-B, C-S, and C-Se.

18.
J Org Chem ; 86(3): 2682-2695, 2021 Feb 05.
Artigo em Inglês | MEDLINE | ID: mdl-33427445

RESUMO

Strain-driven palladium/N-heterocyclic carbene-catalyzed C-C bond activation of diphenylcyclopropenone (DPC) has been explored for one-step access to trisubstituted α,ß-unsaturated esters and amides. The designed transformation works under mild conditions providing exclusively a single stereoisomer. Mechanistic studies support the oxidative addition of the C-C bond of cyclopropenone to in-situ-generated Pd(0) intermediate. We have proved that vinylic hydrogen in the product is coming from phenol/aniline through deuterium-labeling studies. Late-stage functionalization of bioactive molecules such as procaine, estrone, and hymecromone demonstrates the robustness of this protocol.

19.
J Org Chem ; 86(1): 1108-1117, 2021 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-33332119

RESUMO

A Rh-catalyzed pot and step economic synthesis of aza-polycyclic aromatic hydrocarbons (N-PAHs) from readily available aryl ketones and alkynes has been disclosed. Additionally, a novel synthetic application of the well-known aminating reagent hydroxylamine-O-sulfonic acid (HOSA) has been explored as an in situ redox-neutral directing group for the formation of N-PAHs via isoquinoline. Multiple bond formation in a single operation through a cascade of triple C-H bond activations is the beauty of this protocol. The challenging annulations of two different alkynes in a regioselective fashion have been demonstrated effectively. Mechanistic studies reveal that 3,4-diphenyl-1-methylisoquinoline is an active intermediate for this one-pot transformation.

20.
J Org Chem ; 86(1): 1074-1083, 2021 01 01.
Artigo em Inglês | MEDLINE | ID: mdl-33351628

RESUMO

A redox neutral Co(III)-catalyzed annulation of α,ß-unsaturated oxime ether with alkyne has been reported. Multisubstituted pyridines were synthesized in good yields without the use of any heavy metal oxidants. The developed methodology tolerates a variety of functional groups. Notably, this transformation has been applied to the late-stage modification of the bioactive molecule dehydropregnenolone.

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