Total Synthesis of (−)‐atrop‐Abyssomicin C

Bihelovic, Filip; Saičić, Radomir N.

doi:10.1002/anie.201108223

Cited by 67 publications

(43 citation statements)

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“…Though concise and relatively high yielding, this synthetic approach has since been paralleled or superseded by alternate strategies; 53 notably Bihelovic and Saicic's approach, which avoids epoxide ring opening of the tetronate in the hope of higher tolerance in the generation of analogues for SAR studies. [54][55][56] Scheme 4: Convergent synthesis of atrop-abyssomicin (24) via connection of spirotetronate intermediate 25 with aldehyde 26 over 6 steps to give 27, which is subjected to ring closing metathesis, oxidation and final deprotection to give 24.…”

Section: Abyssomicin C: a Promising Antibacterial For Tuberculosismentioning

confidence: 99%

A twist of nature – the significance of atropisomers in biological systems

2015

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. (2015). A twist of nature-the significance of atropisomers in biological systems. Natural Product Reports: a journal of current development in bioorganic chemistry, 32 (11), 1562-1583. A twist of nature-the significance of atropisomers in biological systems AbstractRecently identified natural atropisomeric compounds with potential medicinal applications are presented. The ability of natural receptors to possess differential binding between atropisomers is an important factor when considering active and inactive atropisomeric drugs, and has required the development of new techniques for atropselective synthesis of desired targets. Advances in this field therefore have significant relevance to modern pharmaceutical and medicinal chemistry. The atropisomeric natural products discussed include hibarimicinone, flavomannins, talaromannins, viriditoxin, rugulotrosin A, abyssomicin C, marinopyrroles, dixiamycins, streptorubin B, ustiloxins A-F, haouamine A, bisnicalaterines, and tedarene B, all of which show significant potential as leads in antibiotic, antiviral and anticancer studies. The importance for the development of common practices regarding atropisomer recognition and classification is also emphasized. AbstractRecently identified natural atropisomeric compounds with potential medicinal applications are presented. The ability of natural receptors to possess differential binding between atropisomers is an important factor when considering active and inactive atropisomeric drugs, and has required the development of new techniques for atropselective synthesis of desired targets. Advances in this field therefore have significant relevance to modern pharmaceutical and medicinal chemistry. The atropisomeric natural products discussed include hibarimicinone, flavomannins, talaromannins, viriditoxin, rugulotrosin A, abyssomicin C, marinopyrroles, dixiamycins, streptorubin B, ustiloxins A-F, haouamine A, bisnicalaterines, and tedarene B, all of which show significant potential as leads in antibiotic, antiviral and anticancer studies. The importance for the development of common practices regarding atropisomer recognition and classification is also emphasized.

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Section: Abyssomicin C: a Promising Antibacterial For Tuberculosismentioning

confidence: 99%

A twist of nature – the significance of atropisomers in biological systems

2015

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“…Next, attention was turned toward the most abundant sphingosine 2 in nature, which could be obtained through the addition of (E)-1-iodo-1-pentadecene (8) 21 to Garner's aldehyde (1, Scheme 2). With the previously optimized chromium(II) loading, N,O-protected sphingosines 9a and 9b were obtained with an even higher diastereoselectivity (anti:syn = 7:1).…”

Section: Resultsmentioning

confidence: 99%

“…1, 2 The NHK reaction showed good tolerance to a range of functional groups in both reaction partners. The great synthetic potential of the nickel-catalyzed addition of alkenylchromium reagents to aldehydes was demonstrated in the syntheses of various natural products, 3 including palytoxin, 4 halichondrin, 5 epothilone B and D, 6 pestalotiopsin A 7 and abyssomicin C. 8 As alkenylchromium species are less basic than other organometallic reagents, their addition to chiral aldehydes proceed without epimerization at the α carbon atom. 2c While the stereochemical outcome of intermolecular NHK reactions was thoroughly investigated with allylchromium species, 2,9 less attention has been paid to the stereoselectivity of the addition of alkenylchromium nuc-628 FERJANČIĆ, MATOVIĆ and BIHELOVIĆ leophiles.…”

Section: Introductionmentioning

confidence: 99%

“…Intermolecular additions, as well as intramolecular reactions on conformationally more flexible substrates, often result in mixtures of diastereoisomers, sometimes even with a complete lack of diastereoselectivity. 8, 10 Garner's aldehyde (tert-butyl (4S)-4-formyl-2,2-dimethyloxazolidine-3-carboxylate) (1) 11 is a conformationally restricted α-nitrogen-substituted aldehyde, which represents a good substrate for probing the stereochemical outcome of alkenylchromium(III) addition. Nucleophilic additions of various organometallic species to Garner's aldehyde (1) are well studied.…”

Section: Introductionmentioning

confidence: 99%

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Diastereoselective addition of alkenylchromium(III) reagents to Garner’s aldehyde: Nozaki-Hiyama-Kishi coupling approach to sphingosines and ceramides

Ferjancic

Matović²,

Bihelovic

2014

JSCS

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Intermolecular Nozaki-Hiyama-Kishi coupling between alkenylchromium(III) reagents, derived from either (E)-(2-bromoethenyl)benzene or (E)-1-iodo-1-pentadecene, and the conformationally rigid Garner's aldehyde resulted in the stereoselective formation of Felkin-type allylic alcohols in good yields, thus providing an easy access to sphingosines. In addition, when the protecting group in the Garner's aldehyde was changed (from Boc to N-octanoyl), a reversal of stereoselectivity was observed in the reaction with (E)--1-pentadecenylchromium(III), probably as the result of hydrophobic interactions between the long carbon chains of the reaction partners.

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“…Many different strategic approaches for the synthesis of macrocyclic core structures besides the classical lactonization conditions by anhydride‐type activation of the corresponding ω‐seco‐acids have been reported in the recent past, including ring‐closing metathesis,, Diels–Alder macrocyclization, intramolecular cross‐coupling reactions,, metal‐catalyzed coupling reactions,– or Horner–Wadsworth–Emmons‐type olefinations . However, the development of improved strategic approaches to face demands for resource efficiency in organic chemistry for the construction of macrolactones remains a highly active and challenging field of research.…”

Section: Figurementioning

confidence: 99%

The Total Synthesis of Epothilone D as a Yardstick for Probing New Methodologies

Haydl

Breit

2016

Chemistry A European J

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Here, a concise and highly convergent synthesis of epothilone D was investigated, relying on fragments of equal complexity that could be prepared in gram scale quantities. The strategy to construct the fragments includes the use of a previously reported enantiospecific zinc-catalyzed cross-coupling of an α-hydroxy ester triflate with a Grignard reagent, the application of a hydroboration/boron-magnesium exchange sequence for the rapid construction of the Z-substituted trisubstituted double bond present in the natural product, and a Noyori-type hydrogenation to install the β-hydroxy ester moiety of the southern part. The key to success is the diastereoselective head-to-tail macrolactonization by an intramolecular addition of the corresponding ω-alkynyl-substituted carboxylic acids to construct a new stereocenter in the macrocyclic core structure in one single step.

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Total Synthesis of (−)‐atrop‐Abyssomicin C

Cited by 67 publications

References 58 publications

A twist of nature – the significance of atropisomers in biological systems

A twist of nature – the significance of atropisomers in biological systems

Diastereoselective addition of alkenylchromium(III) reagents to Garner’s aldehyde: Nozaki-Hiyama-Kishi coupling approach to sphingosines and ceramides

The Total Synthesis of Epothilone D as a Yardstick for Probing New Methodologies

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