Magnesium Monoperphthalate (MMPP): a Convenient Oxidant for the Direct Rubottom Oxidation of Malonates, β‐Keto Esters, and Amides

Meninno, Sara; Villano, Rosaria; Lattanzi, Alessandra

doi:10.1002/ejoc.202100098

Cited by 4 publications

(3 citation statements)

References 55 publications

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“…2a ). We would like to note that homoallylic alcohol 44 could be prepared in high yield (67–80%) from dimethyl predysiherbol 14 either using magnesium monoperoxyphthalate (MMPP) 20 or trifluoroacetone-oxone-Na 2 EDTA 21 and the isomeric, non-rearranged allylic alcohol 45 could also be prepared from dimethyl predysiherbol 14 through 1 O 2 ene reaction 22 under photochemical conditions in 62% yield (see ESI † for details).…”

Section: Resultsmentioning

confidence: 99%

Divergent total synthesis of the revised structures of marine anti-cancer meroterpenoids (+)-dysiherbols A–E

et al. 2023

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Section: Resultsmentioning

confidence: 99%

Divergent total synthesis of the revised structures of marine anti-cancer meroterpenoids (+)-dysiherbols A–E

et al. 2023

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“…Despite 5α,6α-epoxysteroids have generally been obtained by oxidation with the most common peroxyacid 3-chloroperoxybenzoic acid ( m -CPBA), MMPP has emerged as an advantageous alternative, considering its higher stability in the solid state and safety in handling. In addition, this peroxyacid can be produced and commercialized at a lower cost, and the respective work-up procedures are relatively easy due to its water solubility [ 20 , 36 , 37 , 38 ]. Moreover, MMPP is more selective than m -CPBA considering the obtention of α-epoxides, leading to significantly higher values of α/β epoxide ratios [ 20 , 39 ].…”

Section: Resultsmentioning

confidence: 99%

Synthesis, In Vitro Biological Evaluation of Antiproliferative and Neuroprotective Effects and In Silico Studies of Novel 16E-Arylidene-5α,6α-epoxyepiandrosterone Derivatives

et al. 2023

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Steroids constitute an important class of pharmacologically active molecules, playing key roles in human physiology. Within this group, 16E-arylideneandrostane derivatives have been reported as potent anti-cancer agents for the treatment of leukemia, breast and prostate cancers, and brain tumors. Additionally, 5α,6α-epoxycholesterol is an oxysterol with several biological activities, including regulation of cell proliferation and cholesterol homeostasis. Interestingly, pregnenolone derivatives combining these two modifications were described as potential neuroprotective agents. In this research, novel 16E-arylidene-5α,6α-epoxyepiandrosterone derivatives were synthesized from dehydroepiandrosterone by aldol condensation with different aldehydes followed by a diastereoselective 5α,6α-epoxidation. Their cytotoxicity was evaluated on tumoral and non-tumoral cell lines by the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay. Furthermore, the assessment of the neuroprotective activity of these derivatives was performed in a dopaminergic neuronal cell line (N27), at basal conditions, and in the presence of the neurotoxin 6-hydroxydopamine (6-OHDA). Interestingly, some of these steroids had selective cytotoxic effects in tumoral cell lines, with an IC50 of 3.47 µM for the 2,3-dichlorophenyl derivative in the breast cancer cell line (MCF-7). The effects of this functionalized epoxide on cell proliferation (Ki67 staining), cell necrosis (propidium iodide staining), as well as the analysis of the nuclear area and near neighbor distance in MCF-7 cells, were analyzed. From this set of biological studies, strong evidence of the activation of apoptosis was found. In contrast, no significant neuroprotection against 6-OHDA-induced neurotoxicity was observed for the less cytotoxic steroids in N27 cells. Lastly, molecular docking simulations were achieved to verify the potential affinity of these compounds against important targets of steroidal drugs (androgen receptor, estrogen receptor α, and 5α-reductase type 2, 17α-hydroxylase-17,20-lyase and aromatase enzymes). This in silico study predicted a strong affinity between most novel steroidal derivatives and 5α-reductase and 17α-hydroxylase-17,20-lyase enzymes.

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“…More recently, Lattanzi and co‐workers used the cheap and stable peroxy acid derivative, magnesium monoperphthalate ( 365 ), for the selective α ‐hydroxylation of β ‐keto esters and amides. However, good yields were only observed for the cyclic β ‐keto amides such as 364 (Scheme 72c) [166] …”

Section: Reactivities Of β‐Keto Amidesmentioning

confidence: 99%

β‐Keto Amides: A Jack‐of‐All‐Trades Building Block in Organic Chemistry

Zheng

et al. 2021

Eur J Org Chem

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β‐Keto amides are a versatile class of compounds that find wide applications in organic chemistry owing to the juxtaposition of multiple reaction sites within their molecular structures. Due to the importance of β‐keto amides in modern organic chemistry, numerous novel preparation methods, synthetic applications and unprecedented reactivities have been recorded over the past decade. Taking advantage of transition‐metal‐catalysis and organocatalysis, β‐keto amides have emerged into a jack‐of‐all‐trades building block for many stereoselective or tandemized multicomponent reactions. But so far, no reviews have been documented on these recent achievements with β‐keto amides. Our Review aims to provide a thorough summary regarding: (a) the synthesis of β‐keto amides, (b) the reactivities of β‐keto amides, (c) the synthetic applications of β‐keto amides in various important heterocyclic compounds, and (d) the coordination of β‐keto amides with main group elements and transition metals and the relevant applications.

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Magnesium Monoperphthalate (MMPP): a Convenient Oxidant for the Direct Rubottom Oxidation of Malonates, β‐Keto Esters, and Amides

Cited by 4 publications

References 55 publications

Divergent total synthesis of the revised structures of marine anti-cancer meroterpenoids (+)-dysiherbols A–E

Divergent total synthesis of the revised structures of marine anti-cancer meroterpenoids (+)-dysiherbols A–E

Synthesis, In Vitro Biological Evaluation of Antiproliferative and Neuroprotective Effects and In Silico Studies of Novel 16E-Arylidene-5α,6α-epoxyepiandrosterone Derivatives

β‐Keto Amides: A Jack‐of‐All‐Trades Building Block in Organic Chemistry

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