Synthesis and alkyne-coupling chemistry of cyclomanganated 1- and 3-acetylindoles, 3-formylindole and analogues

Depree, Gary J.; Main, Lyndsay; Nicholson, Brian K.; Robinson, Nicholas P.; Jameson, Geoffrey B.

doi:10.1016/j.jorganchem.2005.09.049

Cited by 15 publications

(4 citation statements)

References 17 publications

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“…Metalorganic chemistry methods was used for the synthesis of substituted 3 H ‐pyrrolo[1,2‐ a ]indoles. The interaction of N ‐acetyl indole manganate 118 with dimethyl acetylenedicarboxylate 101a or diphenylacetylene 119 resulted in the formation of pyrroindoles 120 and byproducts of simple demetalation 121 . Similar transformation in the presence of silver trifluoromethanesulfonate in nonpolar solvents such as petroleum ether and heptane was described in .…”

Section: Introductionmentioning

confidence: 73%

Synthesis and Some Biological Properties of Pyrrolo[1,2‐a]indoles

Monakhova

Ryabova

Makarov

2015

Journal of Heterocyclic Chem

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Section: Introductionmentioning

confidence: 73%

Synthesis and Some Biological Properties of Pyrrolo[1,2‐a]indoles

Monakhova

Ryabova

Makarov

2015

Journal of Heterocyclic Chem

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“…For examples with acyl groups there is insertion into the MneC bond followed by a cyclisation reaction involving the acyl groups to form indenols and related species [14,15,28,29]. In the case of orthomanganated P(OPh) 3 or Ph 3 P]S, insertion reactions with alkynes led to products with enlarged metallocyclic rings [30,31].…”

Section: Reaction With Phcchmentioning

confidence: 99%

An orthomanganation route to 2-substituted derivatives of N-methyl-1,8-naphthalimide

Nicholson¹,

Crosby²,

Maunsell³

et al. 2012

Journal of Organometallic Chemistry

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“…Following Chen and Wang’s “breakthrough” study in 2013 on Mn(I)-mediated C–H bond alkenylation of 2-phenylpyridines, these species have demonstrated a significant potential and versatility as Earth-abundant metal catalysts for applied chemical synthesis . The catalytic chemistry is founded in the stoichiometric organometallic chemistry of manganese, which has been studied for >40 years and has included extensive work on directed cyclomanganation of aromatic C–H bonds , and subsequent reactivity of the resulting manganacycles. , …”

Section: Introductionmentioning

confidence: 99%

Manganese-Mediated C–H Bond Activation of Fluorinated Aromatics and the ortho-Fluorine Effect: Kinetic Analysis by In Situ Infrared Spectroscopic Analysis and Time-Resolved Methods

et al. 2022

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Insights into the factors controlling the site selectivity of transition metal-catalyzed C−H bond functionalization reactions are vital to their successful implementation in the synthesis of complex target molecules. The introduction of fluorine atoms into substrates has the potential to deliver this selectivity. In this study, we employ spectroscopic and computational methods to demonstrate how the "ortho-fluorine effect" influences the kinetic and thermodynamic control of C−H bond activation in manganese(I)mediated reactions. The C−H bond activation of fluorinated N,Ndimethylbenzylamines and fluorinated 2-phenylpyridines by benzyl manganese(I) pentacarbonyl BnMn(CO) 5 leads to the formation of cyclomanganated tetracarbonyl complexes (2a−b and 4a− e), which all exhibit C−H bond activation ortho-to-fluorine.Corroboration of the experimental findings with density functional theory methods confirms that a kinetically controlled irreversible σ-complex-assisted metathesis mechanism is operative in these reactions. The addition of benzoic acid results in a mechanistic switch, so that cyclomanganation proceeds through a reversible AMLA-6 mechanism (kinetically and thermodynamically controlled). These stoichiometric findings are critical to catalysis, particularly subsequent insertion of a suitable acceptor substrate into the C−Mn bond of the regioisomeric cyclomanganated tetracarbonyl complex intermediates. The employment of time-resolved infrared spectroscopic analysis allowed for correlation of the rates of terminal acetylene insertion into the C−Mn bond with the relative thermodynamic stability of the regioisomeric complexes. Thus, more stable manganacycles, imparted by an ortho-fluorine substituent, exhibit a slower rate of terminal acetylene insertion, whereas a para-fluorine atom accelerates this step. A critical factor in governing C−H bond site selectivity under catalytic conditions is the generation of the regioisomeric cyclomanganated intermediates, rather than their subsequent reactivity toward alkyne insertion.

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Synthesis and alkyne-coupling chemistry of cyclomanganated 1- and 3-acetylindoles, 3-formylindole and analogues

Cited by 15 publications

References 17 publications

Synthesis and Some Biological Properties of Pyrrolo[1,2‐a]indoles

Synthesis and Some Biological Properties of Pyrrolo[1,2‐a]indoles

An orthomanganation route to 2-substituted derivatives of N-methyl-1,8-naphthalimide

Manganese-Mediated C–H Bond Activation of Fluorinated Aromatics and the ortho-Fluorine Effect: Kinetic Analysis by In Situ Infrared Spectroscopic Analysis and Time-Resolved Methods

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