A stereoselective decarbonylation of aldehydes

Walborsky, H. M.; Allen, L. E.

doi:10.1016/s0040-4039(01)97841-4

Cited by 31 publications

(13 citation statements)

References 7 publications

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“…Decarbonylation offers a desirable synthetic strategy for the construction of complex organic architectures given the ubiquity of CO units in commercially available starting materials and the facility of carbonyl functional group transformations . The coupling of C–C and C–X bond formation events to decarbonylative processes further extends the utility of these reactions. − Among homogeneous systems employed for aldehyde and ketone decarbonylation, precious metals have found the greatest application dating back to early studies employing Wilkinson’s catalyst. − Since then, increasing efforts with different second and third row transition metals such as Rh, Ru, Ir, and Pd have produced a relatively robust class of catalytic decarbonylation methodologies. − However, the reaction normally requires somewhat forceful conditions (>150 °C), mitigating its usefulness in certain applications. − The majority of mechanistic proposals for the decarbonylation process rely on C–H (aldehyde) or C–X (ester, acid chloride, and others) oxidative addition events. − Consequently, precious metal systems have excelled due to their propensity for two-electron redox processes.…”

Section: Introductionsupporting

confidence: 88%

Aldehyde Decarbonylation by a Cobalt(I) Pincer Complex

et al. 2018

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The cobalt(I) pincer complex, [Co(N2)(CyPNP)] (CyPNP = anion of 2,5-bis((dicyclohexylphosphino)methyl)pyrrole), reacts with aromatic, vinylic, and aliphatic aldehydes to produce the corresponding hydrocarbon products and [Co(CO)(CyPNP)]. The pathway for aldehyde decarbonylation is found to involve initial coordination of the aldehyde to Co(I), followed by oxidative addition of the C–H bond to produce a cobalt(III) acyl hydride. The acyl hydride species then undergoes CO deinsertion, followed by reductive elimination to afford the decarbonylated product and [Co(CO)(CyPNP)]. Reactions of [Co(N2)(CyPNP)] with other carbonyl containing groups such as carboxylic acids and amides also proceed via oxidative addition to give Co(III) intermediates arising from activation of the X–H (X = O or NH) bond. In these cases, however, the Co(III) species extrude molecular hydrogen to produce Co(II) species of the form [Co(X{O}CR)(CyPNP)] (X = O or NH). The ability of [Co(N2)(CyPNP)] to undergo facile oxidative addition is discussed in the context of potential bond activation processes mediated by well-defined Co species.

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Section: Introductionsupporting

confidence: 88%

Aldehyde Decarbonylation by a Cobalt(I) Pincer Complex

et al. 2018

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“…The rate constants (kn = 3.34 X 10-5 sec-1 and kO = 4.75 X 10-6 sec-1) show a primary isotope effect of 7.04. These results are more consistent with a rate-determining concerted'cis elimination reaction of 12 without the intervention of the intermediate alkylrhodium complex (13) than with the two-step mechanism (in which the decomposition of 13 is rate determining) for the following reasons.…”

Section: Resultssupporting

confidence: 57%

“…Although an isotope effect would be expected for a process in which an equilibrium between 12 and 13 is established prior to the rate-determining elimination reaction of 13 to afford styrene and 4, the magnitude of the isotope effect would not be expected to be as large as was observed. With the conversion of 13 to products as the rate-determining step, a measurable concentration of 13 should be observed, yet neither could this intermediate C"D5CD=CH", + DC1 + RhCKCOXPPh,;).…”

Section: Resultsmentioning

confidence: 99%

Mechanism of acid chloride decarbonylation with chlorotris(triphenylphosphine)rhodium(I). Stereochemistry and direction of elimination

Stille¹,

Huang²,

REGAN³

1974

J. Am. Chem. Soc.

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“…It is very important to highlight that decarbonylation with Wilkinson's catalyst occurs with retention of the configuration with high optical purity (Scheme 1). [15a–b] Originally observed by Walborsky and Allen, this valuable reaction outcome additionally promoted the decarbonylation of aldehydes in the synthesis of natural products and complex compounds.…”

Section: Introductionmentioning

confidence: 91%

Application of Transition Metal‐Catalyzed Decarbonylation of Aldehydes in the Total Synthesis of Natural Products

Selaković

Nikolić

Ajdačić³

et al. 2021

Eur J Org Chem

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Decarbonylation is an invaluable reaction, utilized by nature and chemists alike. In different life forms, such as prokaryotes, plants and animals, this transformation is catalyzed by aldehyde decarbonylases. In the laboratory, the transition metal‐catalyzed (TMC) decarbonylation, which was first achieved in 1959, is by and large the dominant way for conducting this reaction. The carbon‐carbon bond cleavage is most often made possible by RhCl(PPh3)3 i. e. Wilkinson's catalyst, but other metals are also used, both in academia and in industry. In this review, we chose to present the applications of TMC decarbonylation in the synthesis of natural products and their derivatives. More than 30 examples are showcased and categorized into three categories based on the essence of the role of the aldehyde group in the synthesis. A short outlook is given in the end, listing the different advantages and disadvantages of Wilkinson's catalyst, as well as offering a brief prospect for the future.

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A stereoselective decarbonylation of aldehydes

Cited by 31 publications

References 7 publications

Aldehyde Decarbonylation by a Cobalt(I) Pincer Complex

Aldehyde Decarbonylation by a Cobalt(I) Pincer Complex

Mechanism of acid chloride decarbonylation with chlorotris(triphenylphosphine)rhodium(I). Stereochemistry and direction of elimination

Application of Transition Metal‐Catalyzed Decarbonylation of Aldehydes in the Total Synthesis of Natural Products

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