Perfluorobutyrate

Perfluorobutyric acid [375-22-4] M 214.0, m -17.5", b 120"/735mm, d 1.651, n 1.295, -0.17. Fractionally distd twice in an Oldershaw column with an automatic vapour-dividing head, the first distn in the presence of cone H2SO4 as a drying agent. 

The aqua ion as a ligand is discussed in section 4.5. Silver forms a range of light-sensitive, insoluble carboxylates that find application in the synthesis of, for example, alkyl halides and esters. The benzoate, trifluoroacetate and perfluorobutyrate have dimeric structures others are polymers (Figure 4.6). 

CO to generate acetic acid in aqueous conditions by means of several catalysts (Table 2.2).26 RhCl3 catalyzed the direct formation of methanol and acetic acid from methane, CO, and O2 in a mixture of perfluorobutyric acid and water with a turnover rate at approximately 2.9 h-1 based on Rh at 80-85°C.27 Under similar conditions, ethane was more active and gave ethanol, acetic acid, and methanol. 

Mejia-Oneto and Padwa have described the rhodium(II) perfluorobutyrate-cata-lyzed decomposition of an a-diazo ketoamide precursor (Scheme 6.78) [163], Micro-wave heating of a solution of the diazo compound in benzene with a catalytic... 

Perfluorobutyric or trifluoroacetic acid may be used in place of trichloroacetic acid. Strong mineral acids and acetic acid are wholly unsatisfactory. If a catalyst is not used, the product is of poor quality and the yield only 30%. Trichloroacetic acid is conveniently added as a solution in tetrahydrofuran (0.01 g./ml.). 

The rhodium(II)-catalyzed reaction of propargyl compounds 169 and diazo compounds 170 gave corresponding functionalized allenes 171 together with cydopro-penes 172 (Scheme 3.87) [126]. Rh2(pfb)4, where pfb represents perfluorobutyrate, was found to be an excellent catalyst for preparing the allenes 171. An analogous rhodium(II) complex, Rh2(OAc)4, afforded mainly 172 with only a trace amount of 171 (<5%). 

O, O Carboxylic acid, RCOOH e.g., perfluorobutyric (C3F7COOH), salicylic CsHtCOHlCOOH, cinnamic (C6H5(CH)2C00H) acids... 

The development of the first alkyne silylformylation reaction was reported in 1989 by Matsuda [27]. Alkynes were treated with Me2PhSiH and Et3N with 1 mol% Rh4(CO)i2 under CO pressure to produce yS-silyl-a,/ -unsaturated aldehydes (Scheme 5.20). A second report from Ojima detailed the development of rhodium-cobalt mixed metal clusters as effective catalysts for alkyne silylformylation [28]. Shortly thereafter, Doyle reported that rhodium(II) perfluorobutyrate was a highly efficient and selective catalyst for alkyne silylformylation under remarkably mild reaction conditions (0°C, 1 atm CO) [29]. In all these reports, terminal alkynes react regiospedfically with attachment of the silane to the unsubstituted end of the alkyne. The reaction is often (but not always) stereospecific, producing the cis-product preferentially. 

Transition metal-catalyzed intermolecular [2 + 2 + 2] cyclotrimerization of alkynes to benzene derivatives has been extensively studied. In this section, the focus is on the cyclo-trimerizations of the substrates bearing three independent unsaturated bond components. The key issue with this type of process usually involves the challenge of controlling regioselectivity [1—1]. However, 1,3,5-trisubstituted benzene 44 can be obtained as the sole product in good yield when 3-butyn-2-one 43 is used as the substrate for the cyclotrimerization catalyzed by Rh2(pfb)4 (pfb=perfluorobutyrate) in the presence of EtsSiH under a CO atmosphere (Eq. 11) [30]. 

Carbonyl ylides possess versatile reactivities, among which the 1,3-dipolar cycloaddition is the most common and important reaction. The reaction sequence of ylide formation and then 1,3-dipolar cycloaddition can occur in either inter- or intramolecular manner. When the reaction occurs intermolecularly, the overall reaction is a one-pot three-eomponent process leading to oxygen-containing five-membered cyclic compounds, as demonstrated by the example shown in Scheme 8. A mixture of diazo ester 64, benzaldehyde, and dimethyl maleate, upon heating to reflux in CH2CI2 in the presence of 1 mol% rhodium(ii) perfluorobutyrate [Rh2(pfb)4], yields tetrahedrofuran derivative 65 in 49% yield as single diastereomer. " ... 

Thus changing the ligands on dirhodium(II) can provide a switch which, in some cases, can turn competitive transformations on or ofT146. Other examples include the use of dirhodium(II) carboxamides to promote cyclopropanation and suppress aromatic cycloaddition146. For example, catalytic decomposition of diazoketone 105 with dirhodium(II) caprolactamate [Rh2(cap)4] provides only cyclopropanation product 106. In contrast, dirhodium(II) perfluorobutyrate [Rh2(pfb)4] or dirhodium(II)triphenylacetate [Rh2(tpa)4] gave the aromatic cycloaddition product 107 exclusively (equation 100)l46 148. Although we have already seen that rhodium(II) acetate catalysed decomposition of diazoketone 59, which bears both aromatic and olefinic functionalities, afforded stable norcaradiene 60 (equation 70)105, the rhodium(II) acetate catalysed carbenoid transformation within an acyclic system (108) showed no chemoselectivity (equation 101). However, when dirhodi-um(II) carboxamides were employed as catalysts for this type of transformation, only cyclopropanation product 109 was obtained (equation 101). ... 

For the transition-metal catalyzed decomposition of silyl-substituted diazoacetates 205 [silyl = SiMe3, SiEt3, SiMeiBu-i, SitPr-i SiPtnBiW, SiMe2SiMe3], copper triflate and dirhodium tetrakis(perfluorobutyrate) proved to be the best catalysts114. While these two catalysts induce the elimination of N2 at 20 °C even with bulky silyl substituents, dirhodium-tetraacetate even at 100 °C decomposes only the trimethylsilyl-and triethylsilyl-diazoacetates. When the decomposition reactions are carried out in... 

With dirhodium tetrakis(perfluorobutyrate) as catalyst, only ketene 209 was obtained in practically all cases, except for the trimethylsilyl (unseparated product mixture) and triisopropylsilyl cases (no decomposition by this catalyst). 

The decomposition of 368 catalysed by Rh perfluorobutyrate and subsequent intramolecular cycloaddition give 370 in high yield (93%) as the key step in the total synthesis of lysergic acid (371), and is believed to involve the intramolecular reaction of the ylide intermediate 369 at the alkene. No C—H insertion takes place [122], Another elegant example is the efficient construction of the aspidosperma alkaloid skeleton 374. The Rh-catalysed domino cyclization cycloaddition of diazo irnide 372 afforded cycloadduct 374 in 95% yield as a single diastereomer via the dipole 373, and desacetoxy-4-oxo-6,7-dihydrovindorosine (375) has been synthesized from 374 [123]. 

Rhodium(ll) perfluorobutyrate, Rh2(pfb)4. This reagent is obtained as a bright yellow-green solid by transesterification of Rh2(0Ac)4 with perfluorobutyric acid and the anhydride. 

Alcoholysis of R3SiH.1 Rhodium(II) perfluorobutyrate is more effective than Rh2(OAc)4 as a catalyst for reaction of primary or secondary alcohols with trialkyl-silanes at 25° to form silyl ethers. Tertiary alcohols are inert under these conditions. Selective reactions with only primary alcohols can be realized with r-butyldimethyl-silane but not with dimethylphenylsilane. 

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