Pyrroles and Indolizidines from Deprotonated α-(Alkylideneamino)nitriles

Schäfer, Ines; Opatz, Till

doi:10.1055/s-0030-1260415

Cited by 14 publications

(6 citation statements)

References 29 publications

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“…for the construction of γ-amino acids [32], pyrrolidines [33], as well as pyrroles [34–35]. If an additional conjugated double bond is present, the anions of α-(alkylideneamino)nitriles 3 can undergo an electrocyclic ring closure to furnish 3,4-dihydro-2 H -pyrrole-2-carbonitriles 6 after reprotonation [36].…”

Section: Introductionmentioning

confidence: 99%

Simple two-step synthesis of 2,4-disubstituted pyrroles and 3,5-disubstituted pyrrole-2-carbonitriles from enones

Kucukdisli¹,

Ferenc²,

Heinz³

et al. 2014

Beilstein J. Org. Chem.

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Section: Introductionmentioning

confidence: 99%

Simple two-step synthesis of 2,4-disubstituted pyrroles and 3,5-disubstituted pyrrole-2-carbonitriles from enones

Kucukdisli¹,

Ferenc²,

Heinz³

et al. 2014

Beilstein J. Org. Chem.

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“…Initially, our efforts were based on the construction of 3-(aminoalkylidene)oxindoles from the reaction between a propiolamide derivative and an amine. Toward this objective, a model reaction was performed between propiolamide 7a and amine 8 for the synthesis of 9 using various reaction conditions (Table ). The catalytic activity of different catalysts like Pd 2 (dba) 3 , Pd(OAc) 2 , and Pd(PPh 3 ) 4 was first examined in various solvents including toluene, acetonitrile, and dioxane at various temperature without using any additive or ligands (entries 1–8, Table ).…”

Section: Results and Discussionmentioning

confidence: 99%

Stereoselective Construction of 3-(Aminoalkylidene)oxindoles in One Pot: Development of a Novel, Robust, and Scalable Process for the Multigram-Scale Preparation of Nintedanib

Maji,

Halder,

Sharma

et al. 2024

Org. Process Res. Dev.

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A palladium-catalyzed novel stereoselective Heck/Buchwald−Hartwig cascade reaction of substituted N-(2iodophenyl)propiolamides and amines has been established to furnish a series of 3-(aminoalkylidene)oxindole scaffolds with good yields. In addition, we report the development of a robust, scalable, and convergence approach leading to the synthesis of nintedanib (1). Salient features of the approach include the production of key oxindole intermediate 17 via our advanced Heck/Buchwald− Hartwig reaction cascade, which enables the reduction of the number of synthetic steps. Moreover, our approach avoids the expensive column chromatography purification method for all synthetic steps. Further, we also disclosed an alternative route toward the synthesis of another kinase inhibitor hesperadin (2) following the above-mentioned cascade method.

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“…The synthesis of pyrrole via [3 + 2] cycloaddition between imine and alkyne has been reported, however, it usually needs electron withdrawing substituents such as carbonyl and nitrile in the imine compounds or toxic KCN as catalyst. [30][31][32] The intensities of fragments [I(Mn)À Cl] + and [II + H] + decreased at 6 h, indicating their further transformation to the following intermediates such as C and D(Mn). At 12 h, the intensities of C, D(Mn), and HP gradually increased while those of I(Mn) and II varied slightly, indicating the formation of product 1.…”

Section: Reaction Process Studymentioning

confidence: 99%

Mn(II) Promoted Divergent‐Convergent Domino Reaction Giving Dinuclear Tetrasubstituted Pyrrole Complex

Cai,

Zhao,

Zhang

et al. 2024

Chemistry A European J

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Domino reaction of benzo[d]thiazole‐2‐methylamine (S1) has been developed in the presence of MnCl2·4H2O, leading to tetrasubstituted pyrrole coordinated dinuclear Mn(II) complex 1 ([MnClP]2, P‐ = 2,3,4,5‐tetrakis(benzo[d]thiazol‐2‐yl)pyrrol‐1‐ide). The reaction process has been studied by assigning a series of intermediates based on time‐dependent mass spectrometry, control experiments, crystallography, and density functional theory (DFT) theoretical calculation. A plausible mechanism involving an unprecedented divergent‐convergent domino sequence has been proposed. Compound S1 could be activated by MnCl2·4H2O via coordination, which divergently produces two intermediates imine II (1‐(benzo[d]thiazol‐2‐yl)‐N‐(benzo[d]thiazol‐2‐ylmethyl)methanimine) and alkene C (1,2‐bis(benzo[d]thiazol‐2‐yl)ethene) through oxidative self‐condensation and free radical coupling followed by elimination, respectively. They could then react with each other convergently via formal [3+2] cycloaddition to give deprotonated tetrasubstituted pyrrole coordinated intermediate [MnClP] after aromatization. Dimerization of [MnClP] produces the final product 1. Three C‐C bonds and one C‐N bond are formed through this six‐step domino sequence. The corresponding organic skeleton (HP: 2,2',2'',2'''‐(1H‐pyrrole‐2,3,4,5‐tetrayl)tetrakis(benzo[d]thiazole)) has been obtained from 1 and shows a higher fluorescent quantum yield (52%) than the reported 3,4‐diphenyl substituted analogue 2,2'‐(3,4‐diphenyl‐1H‐pyrrole‐2,5‐diyl)bis(benzo[d]thiazole) (DPB) (42%).

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Pyrroles and Indolizidines from Deprotonated α-(Alkylideneamino)nitriles

Cited by 14 publications

References 29 publications

Simple two-step synthesis of 2,4-disubstituted pyrroles and 3,5-disubstituted pyrrole-2-carbonitriles from enones

Simple two-step synthesis of 2,4-disubstituted pyrroles and 3,5-disubstituted pyrrole-2-carbonitriles from enones

Stereoselective Construction of 3-(Aminoalkylidene)oxindoles in One Pot: Development of a Novel, Robust, and Scalable Process for the Multigram-Scale Preparation of Nintedanib

Mn(II) Promoted Divergent‐Convergent Domino Reaction Giving Dinuclear Tetrasubstituted Pyrrole Complex

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