Reactions of (hydroxymethyl) ferrocene. Esters

Combs, Charles S.; Ashmore, Charles I.; Bridges, Alec F.; Swanson, C. R.; Stephens, William D.

doi:10.1021/jo01275a075

Cited by 3 publications

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“…7 Attempts to form the diacetate 5b by conventional means (Ac 2 O, py, DMAP) were unsuccessful, but it was demonstrated that direct S N 1 reaction in AcOH at 80 °C proceeded cleanly, according to precedent. 8 Rather than isolate the diacetate according to conventional phosphination procedures, 9 diol 5a was converted directly into the desired diphosphine 3 by heating with HPBu t 2 (2 equiv.) in AcOH (80°C , 1 h), isolating the product † in 62% yield by precipitation from MeOH.…”

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confidence: 99%

Synthesis and reactivity of a ferrocene-derived PCP-pincer ligand

et al. 2002

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The 1,3-bis(diphosphinomethyl)ferrocene 3 readily reacts with [(C 2 H 4 ) 2 RhCl] 2 to form an equilibrating pair of diastereomers 8a and 8b by C-H insertion into the ferrocene.Pincer-type ligands have played a significant role in homogeneous catalysis. 1 With the recent development of effective catalysts for dehydrogenation that involve Rh, or more especially Ir, complexes related to compound 1, interest in their application has been heightened. 2 Among the factors that contribute to their reactivity in the critical C-H activation step will be the chelate bite angle and the electronic character of both the s-and n-bonding entities. Synthesis and complexation chemistry of a higher homologue 2 based on cycloheptatriene has already been reported. 3 For these reasons we are interested in the synthesis of the ferrocene analogue 3, and report its successful completion together with some preliminary reactions that demonstrate the access to pincer-type ligation.General methods for the preparation of 1,3-disubstituted ferrocenes are severely lacking. 4 In order to synthesise a suitable precursor, we prepared compound 4 according to published procedures, involving the photochemical displacement of p-xylene from CpFe[p-xylene] + BF 4 2 in the presence of 3-methoxycarbonyl-6-dimethylaminofulvene. 5,6 This was cleanly reduced by LiAlH 4 in refluxing THF to the primary diol 5a in 89% yield. 7 Attempts to form the diacetate 5b by conventional means (Ac 2 O, py, DMAP) were unsuccessful, but it was demonstrated that direct S N 1 reaction in AcOH at 80 °C proceeded cleanly, according to precedent. 8 Rather than isolate the diacetate according to conventional phosphination procedures, 9 diol 5a was converted directly into the desired diphosphine 3 by heating with HPBu t 2 (2 equiv.) in AcOH (80°C , 1 h), isolating the product † in 62% yield by precipitation from MeOH.The new ligand was surveyed for its reactivity towards simple unsaturated metal complexes under mild conditions. A model reaction was first established, using ligand 1b. By NMR (C 6 D 6 , 65 °C, 30 min), displacement of the pincer diamine ligand 10 in 6 by the diphosphine was observed. The formation of complex 7 was inferred, ‡ although it was not isolated. Repeating this reaction with ligand 3 gave no evidence of complexation, however. Reaction of the ferrocene-derived ligand 3 with (PPh 3 ) 3 RuCl 2 or (MeCN) 2 PdCl 2 likewise failed to give characterisable products.When ligand 3 was reacted with [(C 2 H 4 ) 2 RhCl] 2 in CD 2 Cl 2 at ambient temperature a clean transformation occurred within minutes, the product being characterised by NMR and MS. † Initially, two sets of resonances were observed in the 1 H NMR spectrum, in particular two distinct Rh-H signals at ca. 227 ppm. Equilibration occurred over 4 h so that the lower field signal, initially the minor component, became strongly predominant. The equilibration could also be followed by 31 P NMR, it being observed that the signal at 87.5 ppm, decreases monotonically over 3 h as the signal at 93.5 ppm increases. ...

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Synthesis and reactivity of a ferrocene-derived PCP-pincer ligand

et al. 2002

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“…Evaporation of the solvent yielded an oil exhibiting a single peak in the vpc with retention time of 1.5 min at 180°. The oil was evaporatively distilled at 75-80°( 32 mm); Xm.x 238 µ (e 14,160); "1" 6.12, 6.28 µ; nmr, 8 4.69, 4.79 (each d, J = 1.5 cps, >C=CH2), 6.05 (m, CH = CH).…”

Section: Methodsmentioning

confidence: 99%

“…Registry No.-2, 19639-98-6; Alkyl ferrocenylmethyl sulfides have been prepared by reduction of alkyl ferrocenethiolcarboxylates with lithium aluminum hydride in the presence of aluminum chloride. 3 Nesmeyanov has reported the preparation of these compounds from ferrocenylmethanethiol,4 and by decomposition of ferrocenylmethyltrimethylammonium iodide in the presence of aqueous sodium sul- 6 No acetic acid catalyst was used. cene by reaction with alkanethiols in the presence of acetic acid according to the reaction shown.…”

Section: Methodsmentioning

confidence: 99%

Reactions of hydroxymethylferrocene. II. Sulfides

Combs¹,

Ashmore²,

Bridges³

et al. 1969

J. Org. Chem.

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Etherification of Ferrocenyl Alcohol by Highly‐efficient Ytterbium Triflate

et al. 2011

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Nucleophilic substitution of ferrocenyl alcohols with various aliphatic alcohols in the presence of a catalytic amount of ytterbium triflate [Yb(OTf) 3 ] was studied. It was found the unsymmetrical ferrocenyl ethers could be easily obtained in excellent yields when the reactions were performed in primary and secondary alcohols. However, in other organic non-alcoholic solvents such as acetonitrile, the formation of symmetrical ferrocenyl ethers rather than unsymmetrical ones was observed.

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Reactions of (hydroxymethyl) ferrocene. Esters

Cited by 3 publications

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Synthesis and reactivity of a ferrocene-derived PCP-pincer ligand

Synthesis and reactivity of a ferrocene-derived PCP-pincer ligand

Reactions of hydroxymethylferrocene. II. Sulfides

Etherification of Ferrocenyl Alcohol by Highly‐efficient Ytterbium Triflate

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