Thermal and photochemical reactions of η<sup>5</sup>-cyclopentadienyl(naphthoyl)(dicarbonyl)iron complexes with alkynes: formation of benzindenones and dihydropentalenones

Butler, Ian R.; Charland, Jean Pierre; Elliot, J. L.; Houde, Jean; Lindsell, W. Edward; McCullough, Kevin J.; Preston, Peter N.; Rettie, Alan B.

doi:10.1039/p19900002799

Cited by 6 publications

(5 citation statements)

References 18 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The major products isolated were two colourless compounds 28 and 29. The former is similar to one in (14), 31, while the latter is an analogue of the compounds we have previously observed to be found in the case of the Fp-naphthoyl reactions with diphenylacetylene (16). We have conducted preliminary experiments on a substantial variety of Fp-aryl groups such as anisoyl, o-toloyl, 2-nicotinoyl, 2-quinoloyl, o-biphenyl, and in In general it is now possible to predict the expected addition have carried out reactions of Fp-benzoyl with phenylcyclopentenones that will be formed in the reaction of Fp-aryls (ary1)acetylenes (aryl = anisyl, o-tolyl, nicotinyl, 2-quinolyl, with acetylenes, Scheme 13; however, the ratio of isomers o-biphenyl, triphenylsilyl), and observe that in each case the obtained will be determined by the nature of the aryl group.…”

Section: P H C C P Hsupporting

confidence: 53%

“…In our own work, we have carried out several investigations to clarify the mechanistic details of these reactions as well as to exploit their synthetic utility (14)(15)(16). The thermal and photochemical reactions of Fp-(1-and 2-naphthoyls) with diphenylacetylene and 1-phenylprop-2-yne were found to give the products 6 and 7 respectively, in addition to a substantial number of by-products including mono and I , 1'-bis-naphthyl ferrocenes (16) (Scheme 4).…”

Section: Phc= Cphmentioning

confidence: 99%

See 1 more Smart Citation

A deuterium labelling study into the insertion of diphenylacetylenes into iron–aryl bonds

Butler¹,

Elliot²,

Houde³

1990

Can. J. Chem.

Self Cite

View full text Add to dashboard Cite

Can. J. Chem. 68, 1564 (1990).The mechanism of the reaction of dicarbonyl(rls-cyclopentadienyl)phenyliron, 1, with diphenylacetylene to give 2,3-diphenyl-[lH]-inden-1-one has been investigated using a partially deuterated 1. The mechanistic pathway of the reaction is discussed in terms of the labelling of the indenones obtained. The reaction of phenylacetylene with 1 gives a mixture of products including 2,4,6-triphenyl-4'-methylbenzophenone and C-4,C-6a-dihydro-4-(4'-methylphenyl)-2-phenylpentalene(l-r-3aH)one.Key words: indenones, acetylenes, iron, carbonyl.IAN R. BUTLER, JOANNE L. ELLIOT et JEAN HOUDE, JR. Can. J. Chem. 68, 1564 (1990).Utilisant un composk 1 partiellement deutCrt, on a examink le mCcanisme de la reaction du dicarbonyl(r15-cyclopentadiknyl)phCnylfer, 1, avec le diphknylacktylkne qui conduit la 2,3-diphknyl-[1H]-indkn-1-one. On discute des diverses voies mkcanistiques de la rkaction en fonction de la position des marqueurs dans les indenones obtenues. La rkaction du phknylacCtylkne avec le composk 1 conduit i un mklange de produits incluant la 2,4,6-triphknyl-4'-mCthylbenzophCnone et la C-4,C-6a-dihydro-4-(4'-mkthylphknyl)-2-phknylpentalene(l-r-3aH)one.

show abstract

Section: P H C C P Hsupporting

confidence: 53%

Section: Phc= Cphmentioning

confidence: 99%

A deuterium labelling study into the insertion of diphenylacetylenes into iron–aryl bonds

Butler¹,

Elliot²,

Houde³

1990

Can. J. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

“…The same reaction in DMAc (Table S2) affords indene 12a as well, albeit in a lower yield (9%). A reaction between 1a and diphenyl acetylene yielded a mixture of inseparable products due to a large number of aromatic C–H sites available for C–H activation . Furthermore, it turns out that KFp reduces extremely electron-poor dimethyl acetylenedicarboxylate (DMAD), a behavior already encountered before during the synthesis of aryliron(II) complexes.…”

Section: Resultsmentioning

confidence: 96%

“…A reaction between 1a and diphenyl acetylene yielded a mixture of inseparable products due to a large number of aromatic C−H sites available for C− H activation. 54 Furthermore, it turns out that KFp reduces extremely electron-poor dimethyl acetylenedicarboxylate (DMAD), a behavior already encountered before during the synthesis of aryliron(II) complexes. Among other aryl fluorides suitable for coupling at high temperatures, 4-fluorophenyl methyl sulfone also yields a corresponding indene 12b in an isolated 17% yield.…”

Section: ■ Results and Discussionmentioning

confidence: 97%

Fe-Promoted C–F Activation of Aryl Fluorides Enables Heck-Type Coupling with Alkenes and One-Pot Synthesis of Indenes

Radzhabov

Mankad

2023

Organometallics

View full text Add to dashboard Cite

Metal-mediated aryl fluoride activation not only presents challenges because of the thermodynamically robust C–F bond but also provides opportunities to develop C–C coupling reactions with this unconventional electrophile. Here, we report that the metallanucleophile, K[CpFe(CO)2] (KFp), is readily arylated by aryl fluorides to provide CpFe(CO)2Ar (FpAr) complexes under ambient conditions in the absence of any catalyst, contrary to previous literature reports. This C–F activation likely proceeds by a SNAr mechanism rather than the more common oxidative addition pathway for metal-mediated C–F cleavage. Facile access to FpAr derivatives has enabled further development of Fe-promoted coupling reactions of aryl fluorides with alkenes and alkynes. Under stoichiometric Fe conditions, Heck-type coupling reactions with aryl fluoride electrophiles are reported herein. Various aryl fluorides were found to couple with olefins to provide E-alkene products; aliphatic derivatives unexpectedly underwent reduction to 1,2-disubstituted ethane products to varying extents. Aryl fluorides were also found to couple with 5-decyne to yield indene derivatives in a one-pot manner; indenone and indanone products were also observed in selected cases. A mechanistic investigation to identify the apparently potent hydride donor generated under these conditions was conducted, leading to a mechanistic hypothesis involving the intermediacy of metal carbonyl-capped, triple-decker ferrocene compounds as reductants. Despite the involvement of these di-iron intermediates limiting stoichiometric product yields, the observed C–C coupling reactions expand the limits of organofluorine chemistry.

show abstract

“…A reaction between 1a and diphenyl acetylene yielded a mixture of inseparable products, due to a large number of aromatic C-H sites available for C-H activation. 51 Furthermore, it turns out that KFp reduces extremely electron-poor dimethyl acetylenedicarboxylate (DMAD), behavior already encountered before during the synthesis of aryliron(II) complexes. Among other aryl fluorides suitable for coupling at high temperatures, 4fluorophenyl methyl sulfone also yields a corresponding indene 12b in an isolated 17% yield.…”

Section: Fe-promoted Heck-type Coupling Of Aryl Fluorides With Alkenesmentioning

confidence: 99%

Fe-Promoted C-F Activation of Aryl Fluorides Enables Heck-Type Coupling with Alkenes and One-Pot Synthesis of Indenes

Radzhabov

Mankad

2023

Preprint

View full text Add to dashboard Cite

Metal-mediated aryl fluoride activation presents challenges because of the thermodynamically robust C-F bond but also provides opportunities to develop C-C coupling reactions with this unconventional electrophile. Here, we report that the metallanucleophile, K[CpFe(CO)2] (KFp), is readily arylated by aryl fluorides to provide CpFe(CO)2Ar (FpAr) complexes at ambient conditions in the absence of any catalyst, contrary to previous literature reports. This C-F activation likely proceeds by a SNAr mechanism rather than the more common oxidative addition pathway for metal-mediated C-F cleavage. Facile access to FpAr derivatives has enabled further development of Fe-promoted coupling reactions of aryl fluorides with alkenes and alkynes. Under stoichiometric Fe conditions, the first documented examples of Heck-type coupling reactions with aryl fluoride electrophiles are reported herein. Various aryl fluorides were found to couple with olefins to provide E-alkene products; aliphatic derivatives unexpectedly underwent reduction to 1,2-disubsituted ethane products to varying extents. Aryl fluorides were also found to couple with 5-decyne to yield indene derivatives in a one-pot manner; indeneone and indanone products were also observed in selected cases. A mechanistic investigation to identify the apparently potent hydride donor generated under these conditions was conducted, leading to a mechanistic hypothesis involving the intermediacy of metal carbonyl-capped, triple-decker ferrocene compounds as reductants. Despite the involvement of these diiron intermediates limiting stoichiometric product yields, the observed C-C coupling reactions expand the limits of organofluorine chemistry.

show abstract

Thermal and photochemical reactions of η⁵-cyclopentadienyl(naphthoyl)(dicarbonyl)iron complexes with alkynes: formation of benzindenones and dihydropentalenones

Cited by 6 publications

References 18 publications

A deuterium labelling study into the insertion of diphenylacetylenes into iron–aryl bonds

A deuterium labelling study into the insertion of diphenylacetylenes into iron–aryl bonds

Fe-Promoted C–F Activation of Aryl Fluorides Enables Heck-Type Coupling with Alkenes and One-Pot Synthesis of Indenes

Fe-Promoted C-F Activation of Aryl Fluorides Enables Heck-Type Coupling with Alkenes and One-Pot Synthesis of Indenes

Contact Info

Product

Resources

About

Thermal and photochemical reactions of η5-cyclopentadienyl(naphthoyl)(dicarbonyl)iron complexes with alkynes: formation of benzindenones and dihydropentalenones

Cited by 6 publications

References 18 publications

A deuterium labelling study into the insertion of diphenylacetylenes into iron–aryl bonds

A deuterium labelling study into the insertion of diphenylacetylenes into iron–aryl bonds

Fe-Promoted C–F Activation of Aryl Fluorides Enables Heck-Type Coupling with Alkenes and One-Pot Synthesis of Indenes

Fe-Promoted C-F Activation of Aryl Fluorides Enables Heck-Type Coupling with Alkenes and One-Pot Synthesis of Indenes

Contact Info

Product

Resources

About

Thermal and photochemical reactions of η⁵-cyclopentadienyl(naphthoyl)(dicarbonyl)iron complexes with alkynes: formation of benzindenones and dihydropentalenones