A facile access to spiro furanone skeleton based on Pd(II)-mediated cyclization–carbonylation of propargylic esters

Kato, Kanefusa; Nouchi, Hideaki; Ishikura, Keisuke; Takaishi, Satoshi; Motodate, Satoshi; Tanaka, Hikaru; Okudaira, Kazuho; Mochida, Tomoyuki; Nishigaki, Ryuichiro; Shigenobu, Koki; Akita, Hiroyuki

doi:10.1016/j.tet.2005.12.033

Cited by 66 publications

(29 citation statements)

References 58 publications

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“…The cyclic ketals can be easily converted into 2-cyclopentenones, which are useful intermediates of natural products [49]. Later, the same group extended this method to the cyclocarbonylation of propargylic acetates [50], propargylic esters [51], and 2-propargyl-1,3-dione [52,53]. Furthermore, using chiral bisoxazoline ligands, they realized the asymmetric cyclization-carbonylation of 2-alkyl-2-propargylcyclohexane-1,3-diones successfully.…”

Section: Scheme 4 Synthesis Of Four-membered Lactams Via Oxidative Camentioning

confidence: 99%

Synthesis of Functionalized Heterocycles via Oxidative Carbonylation

Xing

2015

Topics in Heterocyclic Chemistry

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With the assistance of a proper oxidant, carbonylation of two nucleophiles can take place directly in carbonylation conditions, which is defined as oxidative carbonylation. This process starts with the reaction of nucleophiles with the metal catalyst in oxidation state (M (n + 2) ), followed by insertion of CO and subsequent reductive elimination, providing the carbonylated products and the metal catalyst in reduction state (M (n) ). The oxidant could reoxidize M (n) to M (n + 2) to promote the catalytic cycle. Oxidative carbonylation avoids the difficult oxidative addition of R-X to metal catalyst, so this kind of carbonylation could proceed in mild conditions. What's more is that oxidative carbonylation doesn't need prefunctionalization of substrates. So, it's no wonder that considerable attention has been drawn to construct important carbonylated compounds through oxidative carbonylation. Particularly, much progress in synthesis of carbonylated heterocycles via oxidative carbonylation has been achieved in the past decades. Here, we summarized the main achievements in this area from 1982 to the beginning of 2015.

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Section: Scheme 4 Synthesis Of Four-membered Lactams Via Oxidative Camentioning

confidence: 99%

Synthesis of Functionalized Heterocycles via Oxidative Carbonylation

Xing

2015

Topics in Heterocyclic Chemistry

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“…[22] www.eurjoc.org Scheme 20. [22] An enantioselective version of this kind of reactivity has been applied to the synthesis of nonracemic bicyclic β-alkoxyacrylates 33 (Scheme 22) starting from 2-alkyl-2-propargylcyclohexane-1,3-diones 32 in the presence of Pd-(TFA) 2 /2,2Ј-isopropylidene-bis[(4R)-4-(3,4-dimethoxyphenyl)-2-oxaxine]. [20] Mechanistically, the reaction is believed to proceed through intramolecular nucleophilic attack of the carbonyl group at the triple bond coordinated to Pd II , followed by MeOH attack at the corresponding oxonium intermediate and alkoxycarbonylation.…”

Section: Oxidative Carbonylation Of Acetylenic Substrates Leading To mentioning

confidence: 99%

Oxidative Carbonylation as a Powerful Tool for the Direct Synthesis of Carbonylated Heterocycles

2012

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“…24) Among them, (17a,20E)-17,20-[(1-methoxyethylidene)bis(oxy)]-3-oxo-19-norpregna-4,20-diene-21-carboxylic acid methylester (YK11) was prepared as follows: A 100 ml two-necked round-bottomed flask, containing a magnetic stirring bar, (CH 3 CN) 2 PdCl 2 (6.5 mg, 0.025 mmol), p-benzoquinone (108.1 mg, 1.0 mmol) and MeOH (7 ml) was fitted with a rubber septum and three-way stopcock connected to a balloon filled with carbon monoxide. The apparatus was purged with carbon monoxide by pumping-filling via the three-way stopcock.…”

Section: Chemicalsmentioning

confidence: 99%

“…Previously, we prepared novel synthetic steroids. 24) In our preliminary screening for novel AR ligands, a steroid compound, (17a,20E)-17,20-[(1-methoxyethylidene) bis(oxy)]-3-oxo-19-norpregna-4,20-diene-21-carboxylic acid methyl ester (YK11), behaved apparently as a partial agonist of AR in an ARE-luciferase reporter assay (unpublished data). We were interested in this partial agonistic nature of YK11.…”

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confidence: 99%

(17.ALPHA.,20E)-17,20-[(1-Methoxyethylidene)bis(oxy)]-3-oxo-19-norpregna-4,20-diene-21-carboxylic Acid Methyl Ester (YK11) Is a Partial Agonist of the Androgen Receptor

Kanno

Hikosaka

Zhang

et al. 2011

Biological & Pharmaceutical Bulletin

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The androgen receptor (AR) is a member of the nuclear receptor (NR) superfamily of ligand-dependent transactivation factors. Androgens such as testosterone and 5-a-dihydrotestosterone (DHT) act as agonists of AR. AR mediates various biological effects such as the development of male reproductive tissues, sexual development, and spermatogenesis. [1][2][3][4] Since androgen declining with age contributes to age-related bone and muscle loss and increase in fat mass, 5) the anabolic effect of androgen is attractive for the maintenance of health. Furthermore, it is known that AR is involved in androgen-dependent prostate cancer growth. Thus, antagonists of AR (flutamide, bicalutamide, and nilutamide) are used in anti-androgen therapy for prostate cancer. 8,9) AR mediates the expression of androgen-regulated genes, as represented by prostate specific antigen (PSA) [10][11][12] and FK506-binding protein 51 (FKBP51). [13][14][15] In the absence of a ligand, AR is localized in the cytoplasm, where it forms complexes with chaperones. Upon ligand binding, AR translocates into the nucleus. Following nuclear translocation, AR binds to androgen responsive elements (ARE) in the promoter regions of its target genes as a homodimer. Generally, the transcriptional activity of nuclear receptors is modulated by their interaction with cofactors such as coactivators and corepressors. [16][17][18][19] The type of ligand that binds to the receptor determines which type of cofactor is chosen. In the case of agonists, AR interacts with coactivators dominantly over corepressors, and vice versa in the case of antagonists.Unlike other nuclear receptors, AR AF2 demonstrates weak transcriptional activity. However, ligand-dependent interaction between NTD and LBD/AF2 (which is termed as the N/C interaction) endows AR with synergistic transactivation potential. [20][21][22][23] Thus, the N/C interaction is important for the ligand-dependent transactivation potential of AR.Synthetic AR ligands are useful for treatment of prostate cancer and age-related diseases such as osteopenia and sarcopenia. Previously, we prepared novel synthetic steroids.24) In our preliminary screening for novel AR ligands, a steroid compound, (17a,20E)-17,20-[(1-methoxyethylidene) bis(oxy)]-3-oxo-19-norpregna-4,20-diene-21-carboxylic acid methyl ester (YK11), behaved apparently as a partial agonist of AR in an ARE-luciferase reporter assay (unpublished data). We were interested in this partial agonistic nature of YK11. In this report, we will show that YK11 blocks the N/C-interaction required for the full-agonistic function of wild-type AR, inducing selective AR-target genes owing to the constitutive transactivation potential of AF-1 subdomain in endogenous AR-expressing MDA-MB 453 cells. MATERIALS AND METHODS ChemicalsThe compounds tested in our preliminary screening for novel AR ligands were prepared by previously

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A facile access to spiro furanone skeleton based on Pd(II)-mediated cyclization–carbonylation of propargylic esters

Cited by 66 publications

References 58 publications

Synthesis of Functionalized Heterocycles via Oxidative Carbonylation

Synthesis of Functionalized Heterocycles via Oxidative Carbonylation

Oxidative Carbonylation as a Powerful Tool for the Direct Synthesis of Carbonylated Heterocycles

(17.ALPHA.,20E)-17,20-[(1-Methoxyethylidene)bis(oxy)]-3-oxo-19-norpregna-4,20-diene-21-carboxylic Acid Methyl Ester (YK11) Is a Partial Agonist of the Androgen Receptor

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