Intramolecular cyclization of bis-α-diazoketones: a new synthesis of 4-hydroxytropone

Font, Josep; Serratosa, Francesc; Valls, J.

doi:10.1039/c29700000721

Cited by 43 publications

(15 citation statements)

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“…Also the formation of cis-2-cycloheptene-1,4-dione from N 2 CHCO(CH 2 ) 3 COCHN 2 decomposition by copperbronze catalyst has been reported. [6] Apparently, with the copper-based catalysts, the formation of cyclic cis-alkenes is favoured only for the N 2 CHCO(CH 2 ) n COCHN 2 precursors whose short chain length (n ϭ 3 or 4) prevents the formation of the trans product, for steric reasons.…”

Section: Catalytic Decomposition Of αω-Bis(diazo) Ketonesmentioning

confidence: 99%

Functionalisedcis-Alkenes from the Stereoselective Decomposition of Diazo Compounds, Catalysed by [RuCl(η5-C5H5)(PPh3)2]

Zotto¹,

Baratta²,

Verardo³

et al. 2000

Eur. J. Org. Chem.

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A catalytic amount of [RuCl(η 5 -C 5 H 5 )(PPh 3 ) 2 ] (1) (0.1 mol-%) at 60°C stereoselectively decomposes α-diazo carbonyl compounds N 2 CHCOR [R = EtO, Me, Et, nPr, iPr, Ph, (CH 2 ) 10 Me, and (CH 2 ) 14 Me] affording quantitatively RCOCH=CHCOR carbene dimers [R = EtO (10), Me (11), Et (12), nPr (13), iPr (14), Ph (15), (CH 2 ) 10 Me (16), and (CH 2 ) 14 Me (17)]. The cis isomer is formed in 95−99% purity, depending on the R group. Under the same experimental conditions, N 2 CHCOR 1 and N 2 CHCOR 2 react in equimolar amounts to give mixtures of unsymmetrical cis-R 1 COCH=CHCOR 2 (18−32), and symmetrical cis-R 1 COCH=CHCOR 1 and cis-R 2 COCH=CHCOR 2 alkenes. The unsymmetrical cis-alkenes 23−32 are formed [a]

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Section: Catalytic Decomposition Of αω-Bis(diazo) Ketonesmentioning

confidence: 99%

Functionalisedcis-Alkenes from the Stereoselective Decomposition of Diazo Compounds, Catalysed by [RuCl(η5-C5H5)(PPh3)2]

Zotto¹,

Baratta²,

Verardo³

et al. 2000

Eur. J. Org. Chem.

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“…We initiated our studies by first examining the Rh(II)-catalyzed chemistry of 3-diazo-1-(ethyl 2-diazomalonyl)-indolin-2-one ( 13 ) for several reasons. First, it is already known that bis-diazo containing substrates are prone to undergo ring formation through a metathesis reaction at the diazo carbons . By positioning the D/A diazo moiety in a ring having a 1,3-relationship to the other diazo group, ring formation is not geometrically feasible.…”

Section: Resultsmentioning

confidence: 99%

Polycyclic Ring Formation Using Bis-diazolactams for Cascade Stitching

Bonderoff

Padwa

2016

J. Org. Chem.

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The chemoselective reaction of donor/acceptor (D/A) and acceptor/acceptor (A/A) diazo moieties in the same molecule was examined using 3-diazo-1-(ethyl 2-diazomalonyl)indolin-2-one under rhodium(II) catalysis. The metallo carbenoid derived from the D/A diazo group is preferentially formed and undergoes selective CH, NH, and OH insertion reactions, cyclopropanation, cyclopropenation, sulfur ylide formation/2,3-sigmatropic rearrangement, as well as nitrogen ylide formation followed by azetidine ring expansion. The initial reaction can be paired with a subsequent tandem cascade sequence involving dipole formation/cycloaddition in either an intra- or intermolecular sense to generate polycyclic N-heterocycles in one pot, with the formation up to three new rings in a single operation. Excellent diastereoselectivity was observed in the intramolecular cycloaddition reaction producing 5 to 7-membered rings.

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“…13 The title compound was prepared via the general procedure. After purification by silica gel column chromatography, the product was isolated as a pale yellow oil (18.0 mg, 33% (6), 105 (100), 90 (9), 77 (34); IR (film): 691, 1214, 1285, 1689, 1720 cm −1 .…”

Section: Generalmentioning

confidence: 99%

“…In contrast, the intramolecular carbene dimerization of diazo compounds or their surrogates N-tosylhydrazones, has been developed into useful methods for the construction of cyclic compounds. 6 The mechanism of the transition-metal-catalyzed carbene dimerization of diazo compounds is well established. 4c,d In this process, the transient reactive metal carbene species is firstly formed and subsequently reacts with another diazo substrate (Scheme 1A).…”

Section: Introductionmentioning

confidence: 99%

Catalyst-free cross-coupling of N-tosylhydrazones with chromium(0) Fischer carbene complexes: a new approach to diarylethanone

Yang

Xia

et al. 2015

Org. Chem. Front.

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Intramolecular cyclization of bis-α-diazoketones: a new synthesis of 4-hydroxytropone

Cited by 43 publications

References 0 publications

Functionalisedcis-Alkenes from the Stereoselective Decomposition of Diazo Compounds, Catalysed by [RuCl(η5-C5H5)(PPh3)2]

Functionalisedcis-Alkenes from the Stereoselective Decomposition of Diazo Compounds, Catalysed by [RuCl(η5-C5H5)(PPh3)2]

Polycyclic Ring Formation Using Bis-diazolactams for Cascade Stitching

Catalyst-free cross-coupling of N-tosylhydrazones with chromium(0) Fischer carbene complexes: a new approach to diarylethanone

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