Selective Oxidation of 8,8′-Hydroxylated Binaphthols to Bis-spironaphthalenones or Binaphtho-<i>para</i>- and Binaphtho-<i>ortho</i>-quinones

Podlesny, Erin E.; Carroll, Patrick J.; Kozlowski, Marisa C.

doi:10.1021/ol302195e

Cited by 13 publications

(13 citation statements)

References 33 publications

(29 reference statements)

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“…The molecular structure of 3f is represented in Figure . The bond distances C‐7–Se‐1 [1.856(3) Å], Se‐1–C‐10 [1.916(3) Å] are equal to the characteristic values for a C–Se bond in a ring(1.861–1.887 Å) while the distances O–C‐1 [1.389(4) Å] and O–C‐8 [1.367(4) Å] are in agreement with that reported in the literature (1.376 Å) . The angles involving the bonds C‐7–Se‐1–C‐10 and C‐1–O–C‐8 are 86.96(14)°and 104.59(25)°, respectively.…”

Section: Resultssupporting

confidence: 86%

Iron‐Promoted Tandem Cyclization of 1,3‐Diynyl Chalcogen Derivatives with Diorganyl Dichalcogenides for the Synthesis of Benzo[b]furan‐Fused Selenophenes

et al. 2016

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Ad ouble intramolecular 5-endo-dig cyclization of butyl[2-(phenylbuta-1,3-diynyl)phenyl]chalcogens has been employed in as electivep reparation of benzo[b]chalcogenopheno[2,3-d]furans. Severalr eactionp arameters were studied to determine the best reactionc onditions and we observed that the reactiono fb utyl[2-(phenylbuta-1,3-diynyl)phenyl]chalcogens (0.25 mmol) with iron(III) chloride hexahydrate (2.0 equiv.) and diorganyl diselenides (1.75 equiv.) at reflux of dichloromethane was the most appropriate to give the productsi n3 5-89% yields.T hese standard reactionc onditions were compatible with many functional groups in the substrates,s uch as methyl, chlorine,f luorine,m ethoxy and heteroaryl. This protocolw as also efficient for diorganyl diselenidesb ut it was ineffective with di-organyl disulfidesa nd ditellurides.I nacompetition among selenium, sulfura nd oxygenn ucleophiles we observed that the nucleophilicity and steric effects of the competingf unctional groups were determinant factorsf or the selectivity of the cyclization. Theb enzo[b]chalcogenopheno[2,3-d]furans had absorptions in the UV region (300-350nmr ange) with molar absorptivity coefficient values ascribed to spin and symmetry allowed p-p*e lectronic transitions.A n emission located in the purple region (380-440nm range), with aS tokes shift of between 65-100 nm, is probably associated to the charge transfer character of the excited state.

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Section: Resultssupporting

confidence: 86%

Iron‐Promoted Tandem Cyclization of 1,3‐Diynyl Chalcogen Derivatives with Diorganyl Dichalcogenides for the Synthesis of Benzo[b]furan‐Fused Selenophenes

et al. 2016

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“…An alternate pathway for racemization is also possible through bishemiketal intermediate 39 (Scheme 9, Path B). Formation of this type of structure has been observed with a binaptho- -para -quinone under neutral conditions, 43 as well as an anthraquinone upon treatment with sulfuric acid. 23 Formation of the bishemiketal introduces a bridged biaryl bond, which is known to lower the barrier for atropisomerization.…”

Section: Resultsmentioning

confidence: 94%

Divergent Approach to the Bisanthraquinone Natural Products: Total Synthesis of (S)-Bisoranjidiol and Derivatives from Binaphtho-para-quinones

Podlesny

Kozlowski

2013

J. Org. Chem.

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The development of the first asymmetric synthesis of a chiral anthraquinone dimer is outlined, resulting in the first total synthesis of (S)-bisoranjidiol. Rather than a biomimetic dimerization retrosynthetic disconnection, the anthracenyl ring systems are generated after formation of the axially chiral binaphthalene framework. This synthetic strategy has enabled the synthesis of several analogs. Key features of the synthesis include the enantioselective coupling of a hindered 2-naphthol containing substitution peri to the site of C-C bond formation, the regioselective oxidation of 8,8′-hydroxylated binaphthols to binaphtho-para-quinones, and a tandem regioselective Diels-Alder/aromatization reaction.

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“…8), converting 8,8 0 -hydroxylated binapthols to ortho and para-binaphthoquinones, is achieved using both Co-salen catalyst and IBX. These substrates are able to generate bis-spironaphthalenone compounds via oxidative dearomatization, boosted with PIDA (Podlesny et al, 2012). Biologically active analogs of non-symmetrical alkylhydroxymethoxyquinones can be synthesized from pmethoxyphenol (Fig.…”

Section: Synthetic Methodsmentioning

confidence: 99%

Quinoid systems in chemistry and pharmacology

et al. 2015

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In this paper, we present a brief review of quinoid systems, focusing on their chemical synthesis over the last decade. We address not only major methods of synthesizing quinoids, but also their involvement in biological processes. We highlight their medical relevance and versatility, including antitumor, antiretroviral, or antihypertensive agents, properties determined by their various patterns of substitution. Graphical AbstractKeywords Quinone Á Synthesis Á Cytotoxicity Á Natural products Á Pharmacology Á Redox Abbreviations 3a-HSD 3a-Hydroxysteroid dehydrogenase AIDS Acquired Immune Deficiency Syndrome AlnA Alnumycin A AlnB Alnumycin B BAQ Benzanthracene quinone (7,12-benzo[a] anthraquinone) BPQ Benzo[a]pyrene-7,8-dione CAN Ceric ammonium nitrate CC 50 50 % Cytotoxic concentration CDC25 Cell division cycle phosphatases Cyt Ferricytochrome d-A 2 0 -Deoxyadenosine DBU 1,8-Diazabicyclo[5.4.0]undec-7-ene DDQ 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone d-G, d-Guo 2'-Deoxyguanosine DMF N,N-dimethylformamide DMP Dess-Martin periodinane DMSO

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Selective Oxidation of 8,8′-Hydroxylated Binaphthols to Bis-spironaphthalenones or Binaphtho-para- and Binaphtho-ortho-quinones

Cited by 13 publications

References 33 publications

Iron‐Promoted Tandem Cyclization of 1,3‐Diynyl Chalcogen Derivatives with Diorganyl Dichalcogenides for the Synthesis of Benzo[b]furan‐Fused Selenophenes

Iron‐Promoted Tandem Cyclization of 1,3‐Diynyl Chalcogen Derivatives with Diorganyl Dichalcogenides for the Synthesis of Benzo[b]furan‐Fused Selenophenes

Divergent Approach to the Bisanthraquinone Natural Products: Total Synthesis of (S)-Bisoranjidiol and Derivatives from Binaphtho-para-quinones

Quinoid systems in chemistry and pharmacology

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