Synthesis of indenols and indanones via catalytic cyclic vinylpalladation of aromatic aldehydes

Gevorgyan, Vladimir; Quan, Long Guo; Yamamoto, Yoshinori

doi:10.1016/s0040-4039(99)00656-5

Cited by 135 publications

(52 citation statements)

References 6 publications

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“…Based on the above‐mentioned reports and our own results,5, 8d, 9 the mechanistic study was carried out and is outlined in Scheme . Palladacycle was a reservoir of the catalytically active Pd(0) species.…”

Section: Resultsmentioning

confidence: 99%

Why Does Pivalaldehyde (Trimethylacetaldehyde) Unexpectedly Seem More Basic Than 1‐Adamantanecarbaldehyde in the Gas Phase? FT‐ICR and High‐Level Ab Initio Studies

Quintanilla

Dávalos

Abboud

et al. 2005

Chemistry A European J

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Fourier transform ion cyclotron resonance spectroscopy (FT ICR) techniques, including collision-induced dissociation (CID) methodology, were applied to the study of the gas-phase protonation of pivalaldehyde (1) and 1-adamantanecarbaldehyde (2). A new synthetic method for 2 was developed. The experiments, together with a thorough computational study involving ab initio and density functional theory (DFT) calculations of high level, conclusively show that upon monoprotonation in the gas phase, compound 1 yields monoprotonated methyl isopropyl ketone 3. The mechanism of this gas-phase acid-catalyzed isomerization is different from that reported by Olah and Suryah Prakash for the reaction in solution. In the latter case, isomerization takes place through the diprotonation of 1.

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Section: Resultsmentioning

confidence: 99%

Why Does Pivalaldehyde (Trimethylacetaldehyde) Unexpectedly Seem More Basic Than 1‐Adamantanecarbaldehyde in the Gas Phase? FT‐ICR and High‐Level Ab Initio Studies

Quintanilla

Dávalos

Abboud

et al. 2005

Chemistry A European J

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“…Similar palladium-catalyzed processes (palladium Barbier reactions) are relatively rare (for a review, see [ 18 ]). Early studies were reported by Y. Yamamoto et al [ 19 ] and this group also published examples involving an alkyne palladation step to vinyl palladium intermediates that are able to undergo additions to carbonyl groups [ 20 – 21 ]. Very extensive investigations with a variety of o -haloaniline derivatives as precursors have been reported by the group of Solé, Bonjoch and Fernández [ 22 – 23 ].…”

Section: Discussionmentioning

confidence: 99%

Stereoselective synthesis of tricyclic compounds by intramolecular palladium-catalyzed addition of aryl iodides to carbonyl groups

Saadi¹,

Bentz²,

Redies³

et al. 2016

Beilstein J. Org. Chem.

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SummaryStarting from γ-ketoesters with an o-iodobenzyl group we studied a palladium-catalyzed cyclization process that stereoselectively led to bi- and tricyclic compounds in moderate to excellent yields. Four X-ray crystal structure analyses unequivocally defined the structure of crucial cyclization products. The relative configuration of the precursor compounds is essentially transferred to that of the products and the formed hydroxy group in the newly generated cyclohexane ring is consistently in trans-arrangement with respect to the methoxycarbonyl group. A transition-state model is proposed to explain the observed stereochemical outcome. This palladium-catalyzed Barbier-type reaction requires a reduction of palladium(II) back to palladium(0) which is apparently achieved by the present triethylamine.

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“…Recently, some examples of the insertion of carbonyl groups into late‐transition‐metal–carbon bonds, for example with Rh4 and Ni,5 have been reported, although most of these require the use of stoichiometric organometallic reagents or additives. In palladium chemistry, a limited number of examples catalyzed by Pd 0 have been reported by Vicente,6 Yamamoto,7a–d Yang,8a–c and Larock 8d,e. To the best of our knowledge, there are no examples of the direct insertion of a carbonyl or nitrile group into a carbon–palladium bond by reactions catalyzed by a palladium(II) species through the acetoxypalladation of alkynes.…”

Section: Methodsmentioning

confidence: 99%

Untitled

Zhao

2002

Angew. Chem.

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The insertion of carbon±carbon multiple bonds into car-bon±transition-metal bonds as a facile method of carbon± carbon bond formation is a very important fundamental reaction in transition-metal organometallic chemistry. [1] However, in contrast to the numerous reports regarding the insertion of carbon±carbon multiple bonds into carbon± transition-metal bonds, direct insertion of carbon±heteroatom multiple bonds, such as carbonyl and nitrile groups, without using stoichiometric organometallic reagents, has received scant attention. [1] The disadvantages of such insertion processes are that the carbon±heteroatom p bond is stronger than the carbon±carbon p bond, [2] and that electrophilic metals tend to form s complexes with the heteroatom of carbon± heteroatom multiple bonds, instead of p complexes, [3] which makes the insertion unfavorable. Such obstacles make this area of research particularly challenging. Recently, some examples of the insertion of carbonyl groups into latetransition-metal±carbon bonds, for example with Rh [4] and Ni, [5] have been reported, although most of these require the use of stoichiometric organometallic reagents or additives. In palladium chemistry, a limited number of examples catalyzed by Pd 0 have been reported by Vicente, [6] Yamamoto, [7a±d] Yang, [8a±c] and Larock. [8d,e] To the best of our knowledge, there are no examples of the direct insertion of a carbonyl or nitrile group into a carbon±palladium bond by reactions catalyzed by a palladium(II) species through the acetoxypalladation of alkynes.The fact that a Pd II species is formed after quenching an oxygen±palladium bond through protonolysis, even in Pd 0catalyzed reactions, suggests that a redox system must be involved in the reported Pd 0 -catalyzed carbonyl insertion reactions. It occurs to us that a Pd II -catalyzed reaction may be advantageous for such insertion reactions. Recently, we reported a Pd II -catalyzed cyclization reaction of enyne esters initiated by the acetoxypalladation of alkynes which utilized bipyridine as a ligand. [9] This novel catalytic system encouraged us to develop new reactions using carbon±heteroatom multiple bonds as insertion species, instead of carbon±carbon double bonds. Herein, we wish to exhibit another mechanism involving the cyclization of alkynes with carbonyl or nitrile groups through the acetoxypalladation of alkynes, followed by the insertion of carbon±heteroatom multiple bonds into the carbon±palladium bond and subsequent protonolysis.Our investigation of the reaction conditions began by using dec-2-ynyloxyacetaldehyde (1, 0.5 mmol), Pd(OAc) 2 (5 mol %) as the catalyst, and 2,2'-bipyridine (bpy, 6 mol %) as the ligand in acetic acid (5 mL) at 80 8C (Scheme 1). The reaction afforded products 2±4 (2:3:4 20:40:40) in 78 % total yield. Control experiments confirmed that 4 can partially transform into either 3 (by acetylation) or 2 (by transformation) in this system. Reactions with ketones gave the corresponding tertiary alcohols as a single product in good yield using acetic aci...

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Synthesis of indenols and indanones via catalytic cyclic vinylpalladation of aromatic aldehydes

Cited by 135 publications

References 6 publications

Why Does Pivalaldehyde (Trimethylacetaldehyde) Unexpectedly Seem More Basic Than 1‐Adamantanecarbaldehyde in the Gas Phase? FT‐ICR and High‐Level Ab Initio Studies

Why Does Pivalaldehyde (Trimethylacetaldehyde) Unexpectedly Seem More Basic Than 1‐Adamantanecarbaldehyde in the Gas Phase? FT‐ICR and High‐Level Ab Initio Studies

Stereoselective synthesis of tricyclic compounds by intramolecular palladium-catalyzed addition of aryl iodides to carbonyl groups

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