A Remarkable Glycosidation Reaction: The Total Synthesis of Calicheamicin .gamma.1I

Hitchcock, Stephen A.; Chu-Moyer, Margaret Y.; Boyer, Serge H.; Olson, Steven H.; Danishefsky, Samuel J.

doi:10.1021/ja00126a014

Cited by 59 publications

(39 citation statements)

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“…to provide a-glycoside 95 exclusively (50% over three steps). Global deprotection of 95 involved desilylation with HF$pyridine, cleavage of the dichloroacetyl group with triethylamine in methanol, and hydrolysis of the methoxy acetal with TsOH, leading to apoptolidin(90) in 24% yield (for three steps).Mandelalide A (96) is a novel glycoside of a macrolide which was isolated from Lissoclinum ascidian and showed potent cytotoxicity against human NCI-H460 lung cancer cells (IC50 ¼ 12 nM). The proposed structure of mandelalide A was synthesized by Fürstner et al in 2014, 127 shortly aer, Ye et al revised the structure via total synthesis (Scheme 22).…”

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confidence: 99%

O-Glycosylation methods in the total synthesis of complex natural glycosides

2015

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The total syntheses of 33 complex natural O-glycosides, such as the glycosides of macrocyclic lactones/lactams, enediynes, angucyclines, and anthracyclines, are highlighted, with a major focus being placed on the O-glycosylation reactions which connect the saccharides and the aglycones. These successful O-glycosylation reactions employ such donors as glycosyl bromides, fluorides, iodides, trichloroacetimidates, N-phenyl trifluoroacetimidates, thioglycosides, sulfoxides, heteroaryl thioglycosides, 1-hydroxyl sugars, 1-O-acetates, and ortho-alkynylbenzoates. Each synthesis is depicted starting from the O-glycosylation of the aglycone (or its precursor); the glycosylation conditions and outcomes (yields and stereoselectivities) are discussed, and the subsequent transformations toward the final target, including the elongation of the glycan, the elaboration of the aglycone, and the protecting group manipulations are also given in detail.

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confidence: 99%

O-Glycosylation methods in the total synthesis of complex natural glycosides

2015

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“…In Cal and Cal θ, the reactive moiety is connected at the equatorial position of sugar A (β anomer). However, derivatives in which the α anomer of the sugar is functionalized (axial position) have been synthetically prepared although the functional effects of such modification have not been fully elucidated yet . Here, we used two derivatives in which the aglycone containing the S‐acetate substitution was introduced to the α anomeric form of the carbohydrate tail.…”

Section: Resultsmentioning

confidence: 99%

“…Calicheamicin γ 1 I , the aryl‐tetrasaccharide as well as Cal θ, NAT α and UNN α were prepared as previously described . Stock solutions (1 mg/ml) were prepared in ethyl acetate and stored at −20°C.…”

Section: Methodsmentioning

confidence: 99%

Novel insights on the DNA interaction of calicheamicin γ₁^I

2015

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Calicheamicin γ1(I) (Cal) is a unique molecule in which a DNA binding motif (aryl-tetrasaccharide) is linked to a DNA cleaving moiety (calicheamicinone). The hallmark of this natural product rests in the impressive optimization of these two mechanisms leading to a drug that is extremely efficient in cleaving DNA at well-defined sites. However, the relative contributions of these two structurally distinct domains to the overall process have not been fully elucidated yet. Here, we used different experimental approaches to better dissect the role of the aryl-tetrasaccharide and the enediyne moieties in the DNA sequence selective binding step as well as the in the cleavage reaction. Our results highlight the remarkable cooperation of the two components in producing an amazing molecular machine. The herein presented molecular details of this concerted mechanism of action can be further applied to rationally design more druggable compounds.

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“…In 1994, Samuel J. Danishefsky and his team published their elegant total synthesis of calicheamicin γ 1 I 42. Over the last few decades, the Danishefsky group has demonstrated their flair and acumen in total synthesis with numerous examples of complex natural products in which they made important contributions to new synthetic methodology and chemical biology.…”

Section: Calicheamicin γ1imentioning

confidence: 99%

Inspirations, Discoveries, and Future Perspectives in Total Synthesis

Nicolaou

2009

J. Org. Chem.

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The last one hundred years have witnessed a dramatic increase in the power and reach of total synthesis. The pantheon of accomplishments in the field includes the total synthesis of molecules of unimaginable beauty and diversity such as the four discussed in this article: endiandric acids (1982), calicheamicin γ 1 I (1992), Taxol ® (1994), and brevetoxin B (1995). Chosen from the collection of the molecules synthesized in the author's laboratories, these structures are but a small fraction of the myriad constructed in laboratories around the world over the last century. Their stories, and the background on which they were based, should serve to trace the evolution of the art of chemical synthesis to its present sharp condition, an emergence that occurred as a result of new theories and mechanistic insights, new reactions, new reagents and catalysts, and new synthetic technologies and strategies. Indeed, the advent of chemical synthesis as a whole must be considered as one of the most influential developments of the twentieth century in terms of its impact on society.

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A Remarkable Glycosidation Reaction: The Total Synthesis of Calicheamicin .gamma.1I

Cited by 59 publications

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O-Glycosylation methods in the total synthesis of complex natural glycosides

O-Glycosylation methods in the total synthesis of complex natural glycosides

Novel insights on the DNA interaction of calicheamicin γ₁^I

Inspirations, Discoveries, and Future Perspectives in Total Synthesis

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A Remarkable Glycosidation Reaction: The Total Synthesis of Calicheamicin .gamma.1I

Cited by 59 publications

References 0 publications

O-Glycosylation methods in the total synthesis of complex natural glycosides

O-Glycosylation methods in the total synthesis of complex natural glycosides

Novel insights on the DNA interaction of calicheamicin γ1I

Inspirations, Discoveries, and Future Perspectives in Total Synthesis

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Product

Resources

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Novel insights on the DNA interaction of calicheamicin γ₁^I