Directed ortho metalation - cross coupling connections. Remote lateral metalation - cyclization of 2-imino-2′-methyl biaryls to 9-aminophenanthrenes. A synthesis of the alkaloid piperolactam C

Benesch, L.; Bury, Paul S.; Guillaneux, Denis; Houldsworth, Stephen J.; Wang, X.; Snieckus, Victor

doi:10.1016/s0040-4039(97)10670-0

Cited by 32 publications

(18 citation statements)

References 22 publications

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“…Similarly, approaches via the biaryl nitriles, oxime ethers, and hydrazones 164 provide a general route to the corresponding 9-aminophenanthrenes 165, including the natural product 166 (Scheme 35). [97] The above CIPE for tolyl groups found advantage in additional syntheses of natural products. Thus a concise and efficient route to eupolauramine (169) involves a key DreM of azabiaryl 167, available by sequential crosscoupling and DoM chemistry, to give lactone 168 after acidcatalyzed cyclization (scheme 36).…”

Section: Angewandte Chemiementioning

confidence: 99%

Beyond Thermodynamic Acidity: A Perspective on the Complex‐Induced Proximity Effect (CIPE) in Deprotonation Reactions

et al. 2004

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The concept of the complex-induced proximity effect (CIPE) in deprotonations is helpful in elucidating the mechanisms involved in carbanion chemistry and in planning organic syntheses. In this Review, the consequences of complexation of organolithium bases to functional groups of the substrates before the proton-transfer step are discussed. Experimental data from kinetic measurements and isotope-labeling experiments as well as the results of calculations in many cases point to a prelithiation complex as a reaction intermediate. Some examples from natural products synthesis illustrate how this concept can be used to obtain intermediates in a regio- or stereoselective manner. Of particular interest is the functionalization of positions that are remote from the coordination group.

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Section: Angewandte Chemiementioning

confidence: 99%

Beyond Thermodynamic Acidity: A Perspective on the Complex‐Induced Proximity Effect (CIPE) in Deprotonation Reactions

et al. 2004

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“…Aristolactam alkaloids are highly oxygenated phenanthrene lactam natural products 19,20 that display modest biological activity including anticancer activity (Figure 1). 21 Some previously reported synthetic approaches to the aristolactam alkaloids include: (1) photocyclization of isoindolinones; 22 (2) iodocyclization of alkynylbenzamide; 23 (3) Horner olefination-radical cyclization; 24,25 (4) intramolecular aryne cycloaddition; 26,27 (5) carbonylation of aminophenanthrenes; 28 and (6) tandem Suzuki coupling-aldol condensation. In our retrosynthetic analysis aimed at the construction of the aristolactam alkaloids (Scheme 2), the fused lactam ring can be derived from an amidation of the corresponding fused lactone ring.…”

Section: Scheme 1 Stereochemical and Regiochemical Outcomes Of Tandementioning

confidence: 99%

Investigating the stereochemical outcome of a tandem cyclization-coupling reaction leading to a 3-arylideneisobenzofuran-1-one

Moore¹,

Ohman²,

Garman³

et al. 2018

Arkivoc

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A palladium-catalyzed tandem cyclization-coupling reaction of o-ethynylbenzoic acids with p-iodoanisole led to a stereochemical mixture of 3-arylmethylideneisobenzofuran-1-ones. The major product resulted from an unexpected syn addition of the aryl group and carboxylic acid across the alkyne. Treatment of the major product with the hypervalent iodine reagent (bis(trifluoroacetoxy)iodo)benzene (phenyliodine bis(trifluoacetate)) (PIFA) led to an alkene isomerization that produced the minor tandem product. The structure and stereochemistry of the major and minor tandem reaction products were confirmed by independent syntheses. This work provides access to both the (E) and (Z) stereoisomers of arylmethylideneisobenzofuran-1-ones (phthalides).

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“…A beautiful application of a directed ortho -metalation (DoM) strategy was reported in the synthesis of piperolactam C ( 131 ) by Snieckus (Scheme 16) [113]. Treatment of 129 with base afforded aminophenanthrene 130 via a remote lateral metalation–cyclization sequence.…”

Section: Reviewmentioning

confidence: 99%

The chemistry of isoindole natural products

Speck¹,

Magauer²

2013

Beilstein J. Org. Chem.

302

163

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SummaryThis review highlights the chemical and biological aspects of natural products containing an oxidized or reduced isoindole skeleton. This motif is found in its intact or modified form in indolocarbazoles, macrocyclic polyketides (cytochalasan alkaloids), the aporhoeadane alkaloids, meroterpenoids from Stachybotrys species and anthraquinone-type alkaloids. Concerning their biological activity, molecular structure and synthesis, we have limited this review to the most inspiring examples. Within different congeners, we have selected a few members and discussed the synthetic routes in more detail. The putative biosynthetic pathways of the presented isoindole alkaloids are described as well.

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Directed ortho metalation - cross coupling connections. Remote lateral metalation - cyclization of 2-imino-2′-methyl biaryls to 9-aminophenanthrenes. A synthesis of the alkaloid piperolactam C

Cited by 32 publications

References 22 publications

Beyond Thermodynamic Acidity: A Perspective on the Complex‐Induced Proximity Effect (CIPE) in Deprotonation Reactions

Beyond Thermodynamic Acidity: A Perspective on the Complex‐Induced Proximity Effect (CIPE) in Deprotonation Reactions

Investigating the stereochemical outcome of a tandem cyclization-coupling reaction leading to a 3-arylideneisobenzofuran-1-one

The chemistry of isoindole natural products

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