Ligand-Controlled Iron-Catalyzed Coupling of α-Substituted β-Ketoesters with Phenols

Parnes, Regev; Kshirsagar, Umesh A.; Werbeloff, Aviya; Regev, Clil; Pappo, Doron

doi:10.1021/ol301297k

Cited by 59 publications

(36 citation statements)

References 44 publications

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“…Sridhar group and developed a similar reaction. Pappo's group used ligand‐controlled iron‐catalyzed phenols.…”

Section: Direct C–h Transformation By Iron Catalysismentioning

confidence: 99%

Iron‐catalyzed C−H Activation

2016

J Chinese Chemical Soc

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Transition‐metal‐catalyzed C–H activation and C–C formation have been receiving considerable attention because of their high atom economy and synthesis efficiency. Iron is widely used in catalytic reactions because it has the advantages of abundance, low cost, accessibility, and environmental friendliness. In recent years, research on the Fe‐catalyzed C–H activation of C–C formation has made considerable progress. This paper summarizes latest studies on iron‐catalyzed C–H activation, classifies the catalysts according to the different valence states of iron, and expounds the catalytic mechanism.

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“…Sridhar group and developed a similar reaction. Pappo's group used ligand‐controlled iron‐catalyzed phenols.…”

Section: Direct C–h Transformation By Iron Catalysismentioning

confidence: 99%

Iron‐catalyzed C−H Activation

2016

J Chinese Chemical Soc

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“…of t BuOO t Bu and a catalytic amount of 1,10-phenanthroline to produce polycyclic hemiacetals or polycyclic spirolactones (Scheme 30) [56]. Although the addition of 1,10-phenanthroline was not required in some cases, that ligand acted as an accelerator for the CDC reaction and a decelerator for side reaction.…”

Section: Scheme 19mentioning

confidence: 99%

Iron-Catalyzed Cross-Dehydrogenative-Coupling Reactions

Itazaki

Nakazawa

2015

Topics in Organometallic Chemistry

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Cross-dehydrogenative-coupling (CDC) reactions involving C-H bond activation are powerful tools for C-C bond formation and are highly significant from the perspective of atom economy. A variety of carbon-carbon bond-forming reactions utilizing various coupling partners are known today. Iron-catalyzed organic syntheses have attracted considerable attention because iron is an abundant, inexpensive, and environmentally benign metal. This chapter summarizes the development of iron-catalyzed CDC reactions, the reaction mechanism, and the role of the Fe species in the catalytic cycle in the period from 2007 to 2014.

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“…In our method, the introduction of a ligand was found to dramatically improve the chemoselectivity and the efficiency of the reactions and to reduce the formation of Friedel–Crafts by‐products. Our conditions were also applied for the synthesis of benzofuran 4 from ethyl 2‐benzyloxyacetate ( 2 a ) and 2‐naphthol ( 3 a ), giving an improved 68 % yield 12…”

Section: Introductionmentioning

confidence: 99%

“…[12] As a result of this transformation, a new quaternary carbon bond is formed within a polycyclic hemiacetal or polycyclic spirolactone architecture such as 5, which contains the polycyclic core of lachnanthospirone natural product. [12] In our method, the introduction of a ligand was found to dramatically improve the chemoselectivity and the efficiency of the reactions and to reduce the formation of Friedel-Crafts by-products. Our conditions were also applied for the synthesis of benzofuran 4 from ethyl 2-benzyl-A C H T U N G T R E N N U N G oxyacetate (2 a) and 2-naphthol (3 a), giving an improved 68 % yield.…”

Section: Introductionmentioning

confidence: 99%

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Aerobic Iron‐Based Cross‐Dehydrogenative Coupling Enables Efficient Diversity‐Oriented Synthesis of Coumestrol‐Based Selective Estrogen Receptor Modulators

Kshirsagar

Parnes

Goldshtein

et al. 2013

Chemistry A European J

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An iron-based cross-dehydrogenative coupling (CDC) approach was applied for the diversity-oriented synthesis of coumestrol-based selective estrogen receptor modulators (SERMs), representing the first application of CDC chemistry in natural product synthesis. The first stage of the two-step synthesis of coumestrol involved a modified aerobic oxidative cross-coupling between ethyl 2-(2,4-dimethoxybenzoyl)acetate and 3-methoxyphenol, with FeCl3 (10 mol%) as the catalyst. The benzofuran coupling product was then subjected to sequential deprotection and lactonization steps, affording the natural product in 59% overall yield. Based on this new methodology other coumestrol analogues were prepared, and their effects on the proliferation of the estrogen receptor (ER)-dependent MCF-7 and of the ER-independent MDA-MB-231 breast cancer cells were tested. As a result, new types of estrogen receptor ligands having an acetamide group instead of the 9-hydroxyl group of coumestrol were discovered. Both 9-acetamido-coumestrol and 8-acetamidocoumestrol were found more active than the natural product against estrogen-dependent MCF-7 breast cancer cells, with IC50 values of 30 and 9 nM, respectively.

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Ligand-Controlled Iron-Catalyzed Coupling of α-Substituted β-Ketoesters with Phenols

Cited by 59 publications

References 44 publications

Iron‐catalyzed C−H Activation

Iron‐catalyzed C−H Activation

Iron-Catalyzed Cross-Dehydrogenative-Coupling Reactions

Aerobic Iron‐Based Cross‐Dehydrogenative Coupling Enables Efficient Diversity‐Oriented Synthesis of Coumestrol‐Based Selective Estrogen Receptor Modulators

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