Cycloadditions of Carbonyl Ylides Derived from Diazocarbonyl Compounds

Hodgson, David M.; Muthusamy, Sengodagounder

doi:10.1002/0471264180.or080.02

Cited by 25 publications

(21 citation statements)

References 344 publications

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“…Dirhodium(II)‐complex‐catalyzed 1,3‐dipolar cycloaddition reactions of diazocarbonyl compounds are powerful transformations for the construction of complex oxapolycyclic systems,6–8 and catalytic enantioselective reactions employing chiral Rh II carboxylates have been developed 9. 10 In contrast to non‐asymmetric transformations,11–13 enantioselective 1,3‐dipolar cycloaddition reactions of carbonyl ylides with heterodipolarophiles have rarely been explored 14.…”

Section: Methodsmentioning

confidence: 79%

Rhodium(II)‐Catalyzed Enantioselective Synthesis of Troponoids

Murarka¹,

Jia²,

Merten³

et al. 2015

Angewandte Chemie

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We report a rhodium(II)‐catalyzed highly enantioselective 1,3‐dipolar cycloaddition reaction between the carbonyl moiety of tropone and carbonyl ylides to afford troponoids in good to high yields with excellent enantioselectivity. We demonstrate that α‐diazoketone‐derived carbonyl ylides, in contrast to carbonyl ylides derived from diazodiketoesters, undergo [6+3] cycloaddition reactions with tropone to yield the corresponding bridged heterocycles with excellent stereoselectivity.

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Section: Methodsmentioning

confidence: 79%

Rhodium(II)‐Catalyzed Enantioselective Synthesis of Troponoids

Murarka¹,

Jia²,

Merten³

et al. 2015

Angewandte Chemie

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“…Our interest in diazocarbonyl-derived carbonyl ylide cycloadditions initiated in this project also led to the development of catalytic asymmetric variants, but that is another story. 49,50…”

Section: Scheme 47 Reactivity Of Unsaturated Hydrazones 147 With Et 3 Nmentioning

confidence: 99%

Evolution of a Cycloaddition–Rearrangement Approach to the Squalestatins: A Quarter-Century Odyssey

Almohseni¹,

Hodgson

2020

Synlett

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The highs, lows, and diversions of a journey leading to two syntheses of 6,7-dideoxysqualestatin H5 is described. Both syntheses relied on highly diastereoselective n-alkylations of a tartrate acetonide enolate and subsequent oxidation–hydrolysis to provide an asymmetric entry to β-hydroxy-α-ketoester motifs. The latter were differentially elaborated to diazoketones which underwent stereo- and regioselective Rh(II)-catalysed cyclic carbonyl ylide formation–cycloaddition and then acid-catalysed transketalisation to generate the 2,8-dioxabicyclo[3.2.1]octane core of the squalestatins/zaragozic acids at the correct tricarboxylate oxidation level. The unsaturated side chain was either protected with a bromide substituent during the transketalisation or introduced afterwards by a stereoretentive Ni-catalyzed Csp3–Csp2 cross-electrophile coupling.1 Introduction 2 Racemic Model Studies to the Squalestatin/Zaragozic Acid Core3 Asymmetric Model Studies to a Keto α-Diazoester3.1 Dialkyl Squarate Desymmetrisation3.2 Tartrate Alkylation3.2.1 Further Studies on Seebach’s Alkylation Chemistry 4 Failure at the Penultimate Step to DDSQ 5 Second-Generation Approach to DDSQ: A Bromide Substituent Strategy 5.1 Stereoselective Routes to E-Alkenyl Halides via β-Oxido Phosphonium Ylides 5.2 Back to DDSQ Synthesis6 An Alternative Strategy to DDSQ: By Cross-Electrophile Coupling7 Alkene Ozonolysis in the Presence of Diazo Functionality: Accessing α-Ketoester Intermediates8 Summary

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“…In addition, dipolar cycloadditions using chiral substrates for enantioselective synthesis has been extensively explored since the 1990s. 5 Because several reviews and related articles have recently been published dealing with the synthetic aspects of dipolar cycloaddition chemistry for the preparation of natural products, 6,7 this mini-review for Gordon Gribble's upcoming 50 th year retirement is intended to provide a selective rather than an exhaustive survey of the use of both azomethine and carbonyl ylide dipoles for alkaloid synthesis.…”

Section: Introductionmentioning

confidence: 99%

Use of nitrogen and oxygen dipole ylides for alkaloid synthesis

Padwa¹

2018

Arkivoc

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As highlighted in this mini review, a growing area of interest in organic synthesis involves the use of substituted azomethine and carbonyl ylides as 1,3-dipoles for the preparation of alkaloidal natural products. Cascade reactions proceeding by an intramolecular 1,3-dipolar cycloaddition of nitrogen and oxygen dipole ylides are of particular interest to the synthetic organic community because of the increase in molecular complexity involved and the high isolated yields.

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Cycloadditions of Carbonyl Ylides Derived from Diazocarbonyl Compounds

Cited by 25 publications

References 344 publications

Rhodium(II)‐Catalyzed Enantioselective Synthesis of Troponoids

Rhodium(II)‐Catalyzed Enantioselective Synthesis of Troponoids

Evolution of a Cycloaddition–Rearrangement Approach to the Squalestatins: A Quarter-Century Odyssey

Use of nitrogen and oxygen dipole ylides for alkaloid synthesis

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