Microwave-Assisted Wolff Rearrangement of Cyclic 2-Diazo-1,3-Diketones: An Eco-compatible Route to α-Carbonylated Cycloalkanones

Presset, Marc; Coquerel, Yoann; Rodríguez, Jean

doi:10.1021/jo8021567

Cited by 89 publications

(46 citation statements)

References 33 publications

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“…23 Recently, it was demonstrated that such a rearrangement could occur under dielectric heating (microwave irradiation), and that the transient acylketene can be trapped in a domino process with a variety of nucleophiles including alcohols, amines or thiols in nearly quantitative yields to provide a general access to α-carbonylated cycloalkanones (Scheme 10). 24 This approach allowed the easy introduction of chiral auxiliaries (35 and 37 for example), the preparation of otherwise difficultly available compounds (33, 35 and 36 for example), and overall, proved superior to existing approaches in scope and eco-compatibility. …”

Section: Methodsmentioning

confidence: 99%

“…We can highlight here the recent utilization of malonyl dichloride in the key step of a synthetic approach to the polyprenylated phloroglucinol natural product clusianone (24, Scheme 7). Thus, the highly functionalized bicyclo[3.3.1]nonane framework of the natural product can be obtained in a single synthetic operation from the reaction of the silyl enol ether 22 with malonyl dichloride, a precursor of chloroacylketene, to give 23, which was then converted to clusianone (24) in few steps.…”

Section: Other Reactivity Of 13-dicarbonyl Compoundsmentioning

confidence: 99%

“…In addition to their reactions with nucleophiles, 24 acylketenes can react as 1,3-oxadienes in inverse demand hetero-Diels-Alder reactions, and this reactivity was exploited in a domino threecomponent synthesis of oxazinones. Thus, we were able to obtain a series of oxazinones 96 from the microwave irradiation of a 1:1:1 mixture of 2-diazo-1,3-diketone, an aldehyde and a primary amine (Scheme 35).…”

Section: Mcrs Based On Other Reactionmentioning

confidence: 99%

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1,3-Dicarbonyl compounds in stereoselective domino and multicomponent reactions

Bonne¹,

Coquerel²,

Constantieux³

et al. 2010

Tetrahedron: Asymmetry

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163

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Section: Methodsmentioning

confidence: 99%

Section: Other Reactivity Of 13-dicarbonyl Compoundsmentioning

confidence: 99%

Section: Mcrs Based On Other Reactionmentioning

confidence: 99%

See 1 more Smart Citation

1,3-Dicarbonyl compounds in stereoselective domino and multicomponent reactions

Bonne¹,

Coquerel²,

Constantieux³

et al. 2010

Tetrahedron: Asymmetry

Self Cite

163

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“…Among the different approaches considered, microwaves are clearly the most largely used technique. Representative examples are the generation of ammonia from formamide (see Scheme 6(a), for the synthesis of N-heterocycles) (59), the nucleophilic substitution in aromatics (60), and the Wolff rearrangement of diazoketones (see Scheme 6(b)) (61).…”

Section: Analysis Of the Investigated Topicsmentioning

confidence: 99%

Green chemistry: state of the art through an analysis of the literature

Dichiarante

Ravelli

Albini

2010

Green Chemistry Letters and Reviews

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“…In addition, the 2-indanone derivative 5 l proved to be a particularly appropriate substrate for this metal-catalyzed cycloisomerization, thus leading efficiently to the polycylic alcohol 6 l in almost quantitative yield (entry 5). The allenic compound 5 m, having a strained cyclobutanone moiety, [11] was also cleanly Scheme 1. Reactivity of cyclic allenic ketones.…”

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confidence: 99%

Metal‐Triflate‐Catalyzed Synthesis of Polycyclic Tertiary Alcohols by Cyclization of γ‐Allenic Ketones

2014

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It has been established that bismuth(III) triflate catalyzes the cyclization of g-allenic ketones under mild reaction conditions. This reaction allows the selective formation of polycyclic tertiary alcohols from cyclic ketone derivatives. The resulting dienols can engage in stereoselective cycloadditions to efficiently afford complex polycyclic systems.Complex polycyclic molecules have always fascinated organic chemists, and their rapid, reliable, and efficient synthesis constitutes a motivating challenge to accept. Cycloisomerization reactions are undoubtedly powerful and provide a sustainable means to generate molecular complexity with good control of selectivity.[1] In this context, the intramolecular carbonyl-ene reaction represents a very useful tool for the efficient formation of substituted cyclohexanols, [2] and has been widely used in natural product synthesis. Because of the relatively high energetic barrier, carbonyl-ene processes often require high temperatures or the employment of Lewis acids, usually in excess (Prins reaction). Despite its reliability, this reaction presents some important limitations, such as the difficulty in forming five-membered rings because of the higher cyclization energy requirement induced by geometric factors. In addition, ketones are intrinsically much poorer enophiles than aldehydes in these reactions. Cyclizations involving ketone derivatives have been reported [3] and include highly activated ketones such as trifluoromethylketones [4] or a-ketoesters.[5]The cyclization of carbonyl-allene compounds has been mainly studied under thermal, [6] radical, [7] and transitionmetal-catalyzed [8] processes. Herein we present our results concerning the metal-triflate-catalyzed cyclization of g-allenic ketones. We anticipated that allenes could be used as ene components to bias the geometric cyclization for the formation of five-membered rings. Moreover, the higher reactivity of allenes, as compared to alkenes, should allow the reaction with ketones to proceed under mild reaction conditions. We first used the acyclic b-ketoester 1 bearing a pendant trisubstituted allene as a model and assessed its reactivity towards various metal triflate catalysts in nitromethane (Table 1, entries 1-4). A rapid screening highlighted nonexpensive bismuth(III) triflate [9,10] as a very active catalyst at low loading with the total conversion of 1 occurring at À20 8C. Switching solvents from nitromethane to CH 2 Cl 2 considerably slowed down the reaction rate and led to the isolation of the cyclopentadienes 2 b and 2 c in good yield (88 %) at room temperature by using only 1 mol % of bismuth(III) triflate (entry 5). The formation of 2 b could arise from the elusive ene product 2 a undergoing an elimination reaction. Hydration of compound 2 b could lead to the tertiary alcohol 2 c.To prevent the elimination of the alcohol in 2 a, a reaction which is possibly favored by the position of OH group b to the ester, the reactivity of the allenic cyclohexanone derivative 3 was examined (Scheme 1)....

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Microwave-Assisted Wolff Rearrangement of Cyclic 2-Diazo-1,3-Diketones: An Eco-compatible Route to α-Carbonylated Cycloalkanones

Cited by 89 publications

References 33 publications

1,3-Dicarbonyl compounds in stereoselective domino and multicomponent reactions

1,3-Dicarbonyl compounds in stereoselective domino and multicomponent reactions

Green chemistry: state of the art through an analysis of the literature

Metal‐Triflate‐Catalyzed Synthesis of Polycyclic Tertiary Alcohols by Cyclization of γ‐Allenic Ketones

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