Aldehyde C–H activation with late transition metal organometallic compounds. Formation and reactivity of acyl hydrido complexes

Garralda, María A.

doi:10.1039/b817263c

Cited by 92 publications

(70 citation statements)

References 93 publications

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“…We must note here that, in agreement with this proposal, the structurally related phosphino-alcohol derivative [RuCl(η 6 8g On the other hand, the insertion of aldehydes into a metal−hydride bond has shown to be a reliable route to synthesize α-hydroxyalkyl complexes. 28,32 However, as far as we are aware, this is the first time that an α-hydroxyalkyl compound is formed directly from an alcohol precursor.…”

Section: ■ Introductionmentioning

confidence: 95%

C–H versus O–H Bond Activation in Phosphino-alcohol Ligands: Synthesis of the α-Hydroxy-alkyl Ruthenium(II) Derivatives [RuCl{κ²(P,C)-Ph₂PC₆H₄C(R)OH}(η⁶-arene)]

et al. 2015

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The coordination of the phosphino-alcohol ligands 2-Ph2PC6H4CH(R)OH (R = H, Me) onto an arene-ruthenium(II) fragment gave rise to the formation of complexes of general formula [RuCl2{2-Ph2PC6H4CH(R)OH}(η6-arene)] (R = H, arene = C6H6 (3a), p-cymene (3b), mesitylene (3c), C6Me6 (3d); R = Me, arene = p-cymene (5b)). In solution, different isomers were observed depending on the solvent polarity. They arise from the different coordination modes adopted by the phosphino-alcohol: (i) the classical κ1-P mode through the selective coordination of the phosphorus atom, (ii) the establishment of both Ru–P and Cl····H–O interactions, and (iii) the P,O-chelate formation. Treatment of these species with NaPF6 led to the selective formation of the corresponding cationic species [RuCl{κ2-(P,O)-2-Ph2PC6H4CH(R)OH}(η6-arene)][PF6] 6a–d and 7b, respectively. Unexpectedly, under basic conditions these cationic compounds evolved into the neutral α-hydroxy-alkyl derivatives [RuCl{κ2-(P,C)-Ph2PC6H4C(R)OH}(η6-arene)] through a formal C–H bond activation process.

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Section: ■ Introductionmentioning

confidence: 95%

C–H versus O–H Bond Activation in Phosphino-alcohol Ligands: Synthesis of the α-Hydroxy-alkyl Ruthenium(II) Derivatives [RuCl{κ²(P,C)-Ph₂PC₆H₄C(R)OH}(η⁶-arene)]

et al. 2015

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“…Over the past fifty years, activating aldehyde C–H bonds with Rh has been thoroughly investigated (12); however, the resulting acyl–Rh III –hydrides have been trapped mainly by hydroacylation (13) and/or decarbonylation (14,15). This common intermediate is also implicated in hydroformylation, which is practiced on an industrial scale using syngas (16).…”

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confidence: 99%

Rh-catalyzed C–C bond cleavage by transfer hydroformylation

Murphy

Park

Cruz

et al. 2015

Science

221

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The dehydroformylation of aldehydes to generate olefins occurs during the biosynthesis of various sterols, including cholesterol in humans. Here, we implement a synthetic version that features the transfer of a formyl group and hydride from an aldehyde substrate to a strained olefin acceptor. A Rh(Xantphos)(benzoate) catalyst activates aldehyde C–H bonds with high chemoselectivity to trigger C–C bond cleavage and generate olefins at low loadings (0.3 to 2 mol%) and temperatures (22 to 80 °C). This mild protocol can be applied to various natural products and was used to achieve a three step synthesis of (+)-yohimbenone. A study of the mechanism reveals that the benzoate counterion acts as a proton-shuttle to enable transfer hydroformylation.

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“…The results suggest that the aldehyde C–H cleavage is the most likely turnover-limiting step for the coupling reaction. 14 …”

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confidence: 99%

Intermolecular Markovnikov-Selective Hydroacylation of Olefins Catalyzed by a Cationic Ruthenium–Hydride Complex

Kim

2016

ACS Catal.

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The cationic Ru-H complex was found to be an effective catalyst for the intermolecular hydroacylation of aryl-substituted olefins with aldehydes to form branched ketone products. The preliminary kinetic and spectroscopic studies elucidated a ruthenium-acyl complex as the key intermediate species. The catalytic method directly afforded branched ketone products in a highly regioselective manner while tolerating a number of heteroatom functional groups.

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Aldehyde C–H activation with late transition metal organometallic compounds. Formation and reactivity of acyl hydrido complexes

Cited by 92 publications

References 93 publications

C–H versus O–H Bond Activation in Phosphino-alcohol Ligands: Synthesis of the α-Hydroxy-alkyl Ruthenium(II) Derivatives [RuCl{κ²(P,C)-Ph₂PC₆H₄C(R)OH}(η⁶-arene)]

C–H versus O–H Bond Activation in Phosphino-alcohol Ligands: Synthesis of the α-Hydroxy-alkyl Ruthenium(II) Derivatives [RuCl{κ²(P,C)-Ph₂PC₆H₄C(R)OH}(η⁶-arene)]

Rh-catalyzed C–C bond cleavage by transfer hydroformylation

Intermolecular Markovnikov-Selective Hydroacylation of Olefins Catalyzed by a Cationic Ruthenium–Hydride Complex

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Aldehyde C–H activation with late transition metal organometallic compounds. Formation and reactivity of acyl hydrido complexes

Cited by 92 publications

References 93 publications

C–H versus O–H Bond Activation in Phosphino-alcohol Ligands: Synthesis of the α-Hydroxy-alkyl Ruthenium(II) Derivatives [RuCl{κ2(P,C)-Ph2PC6H4C(R)OH}(η6-arene)]

C–H versus O–H Bond Activation in Phosphino-alcohol Ligands: Synthesis of the α-Hydroxy-alkyl Ruthenium(II) Derivatives [RuCl{κ2(P,C)-Ph2PC6H4C(R)OH}(η6-arene)]

Rh-catalyzed C–C bond cleavage by transfer hydroformylation

Intermolecular Markovnikov-Selective Hydroacylation of Olefins Catalyzed by a Cationic Ruthenium–Hydride Complex

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C–H versus O–H Bond Activation in Phosphino-alcohol Ligands: Synthesis of the α-Hydroxy-alkyl Ruthenium(II) Derivatives [RuCl{κ²(P,C)-Ph₂PC₆H₄C(R)OH}(η⁶-arene)]

C–H versus O–H Bond Activation in Phosphino-alcohol Ligands: Synthesis of the α-Hydroxy-alkyl Ruthenium(II) Derivatives [RuCl{κ²(P,C)-Ph₂PC₆H₄C(R)OH}(η⁶-arene)]