Construction of Quaternary Carbon Stereocenter of α-Tertiary Amine through Remote C–H Functionalization of Tris Derivatives: Enantioselective Total Synthesis of Myriocin

Miyagawa, Takashi; Inuki, Shinsuke; Oishi, Shinya; Ohno, Hiroaki

doi:10.1021/acs.orglett.9b01778

Cited by 12 publications

(7 citation statements)

References 43 publications

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“…Inuki, Ohno, and teammates accomplished the enantioselective total synthesis of myriocin 834 by exploiting the cross metathesis (Scheme 130), a sphingosine analogue isolated from Mycelia sterilia which exhibits strong immunosuppressive activity. [311] Here, the Sharpless asymmetric dihydroxylation of alkene 829 resulted a diol 830, which was then converted to the terminal alkene derivative 831 in several steps. Next, cross metathesis between 831 and acetonide 832 performed with the usage of HG-II catalyst furnished an internal alkene system 833 in 80% yield.…”

Section: Reviewmentioning

confidence: 99%

Metathesis Reactions in Natural Product Fragments and Total Syntheses

et al. 2022

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The passion of total‐ and fragments syntheses of natural products always remained one of the top priorities among the synthetic chemists worldwide. Due their curiosity toward the complexity of molecules of living nature and their endeavour to imitate them in laboratory; limitless arrays of natural products have been extracted, architecturally‐elucidated, synthesized, and chronicled by utilizing various synthetic methodologies in different fashions. Frequently, the synthesis of complex natural products proceed with inscrutable synthetic challenges, which can be circumvented either by modification of previously developed synthetic methods or by formulating a new one. In this way, a myriad of powerful synthetic reactions have been developed since the genesis of the logic of chemical synthesis. Amongst them, metathesis tactics discovered unexpectedly in the 1950s (Nobel Prize in 2005), have incredibly influenced and changed the landscape of the art of the total and formal synthesis in the last three A. H. Hoveyda, A. R. Zhugralin, me abruptly as compared to other developed transformations or their modified forms. In this particular review article, we envisioned to report a comprehensive detail of the metathetic tools involved in both total and fragments synthesis of natural products in the years 2018 and 2019 along with an overview of 2017.

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Section: Reviewmentioning

confidence: 99%

Metathesis Reactions in Natural Product Fragments and Total Syntheses

et al. 2022

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“…Because of their coordination capacity and high affinity through their polar functional groups towards biogenic chiral building blocks of cells, aminodiols and aminotriols are of increasing importance, not only as building blocks but also because of their significant biological activities. For example, pactamycin, the most structurally intricate aminocyclopentitol antibiotic, displays potent antiproliferative properties [ 7 ], whereas the immunosuppressant antibiotic myriocin [ 8 , 9 ] and penaresdin A and B were identified as potent actomyosin ATP-ase activators [ 10 ]. A large majority of these compounds are derived from commercially available monoterpenes, such as (–)-isopulegol, α- or β-pinene [ 6 , 11 ], while only a handful of chiral sources of diterpenes are commercially available in a large scale [ 12 , 13 , 14 ].…”

Section: Introductionmentioning

confidence: 99%

“….5. (4R,6aR,7R,8R,9S,11bS)-Methyl 8-(((4-Fluorobenzyl)amino)methyl)-7,8,9-trihydroxy-4,11b-dimethyltetradecahydro-6a,9-methanocyclohepta[a]naphthalene-4-carboxylate(9) The reaction was accomplished with 4-fluorobenzylamine, as described in the general procedure. Yield: 126 mg (95%); white crystals; m.p.…”

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confidence: 99%

Stereoselective Synthesis and Antiproliferative Activities of Tetrafunctional Diterpene Steviol Derivatives

Bai

Schelz

Erdős

et al. 2023

IJMS

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A new family of diterpene-type aminotriol derivatives has been synthesised from stevioside in a stereoselective manner. The key intermediate spiro-epoxide was prepared through the methyl ester of the allilyc diol derived from steviol. The oxirane ring was opened with primary and secondary amines, providing a versatile library of aminotriols. The corresponding primary aminotriol was formed by palladium-catalysed hydrogenation, and an N,O-heterocyclic compound was synthesised in a regioselective reaction. All new compounds were characterised by 1D- and 2D-NMR techniques and HRMS measurements. In our in vitro investigations, we found that the aromatic N-substituted derivatives exhibited high inhibition of cell growth on human cancer cell lines (HeLa, SiHa, A2780, MCF-7 and MDA-MB-231). The antiproliferative activities were assayed by the MTT method. Furthermore, the introduction of an additional hydroxy group slightly increased the biological activity. The drug-likeness of the compounds was assessed by in silico and experimental physicochemical characterisations, completed by kinetic aqueous solubility and in vitro intestinal-specific parallel artificial membrane permeability assay (PAMPA-GI) measurements.

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“…Their integration in cascade processes is of high synthetic value for the construction of complex molecules, which allows access to untapped chemical space. [1][2][3][4][5][6][7][8] Although the development of cascade reactions involving hydrogen atom transfer [9][10][11][12] or carbene/nitrene insertion [13,14] is making great strides, functionalizations via hydride abstraction in an internal redox process are developing at a comparatively sluggish rate. [15][16][17][18][19][20][21] The emerging growth of gold catalysis has played an important role in cascade reactions involving a C(sp 3 )-H functionalization step.…”

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confidence: 99%

Gold(I)-Catalyzed Benzylic C(sp3)-H Functionalizations: Product Bifurcation towards Indole[a]- and [b]-Fused Polycycles

Greiner

Arichi

Inuki

et al. 2022

Preprint

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Phenylazides substituted by an (alkylphenyl)ethynyl group facilitate divergent benzylic sp3(C-H) functionalization in the presence of a JohnPhosAu catalyst, via N- or C-cyclization, resulting in indole-fused tetra- and pentacycles. The chemoselectivity is influenced depending on the counter-anion (SbF6 or BARF), the electron density of the alpha-imino gold(I) carbene, and the alkyl groups stabilizing the benzylic carbocation originating from a 1,5-hydride shift. An isotop-ic labeling experiment demonstrates the involvement of an indolylgold(I) species resulting in a tautomerization that is much faster than deauration is. The formation of a benzylic sp3(C-H) functionalization resulting in an indole-fused sev-en-membered ring is also demonstrated.

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Construction of Quaternary Carbon Stereocenter of α-Tertiary Amine through Remote C–H Functionalization of Tris Derivatives: Enantioselective Total Synthesis of Myriocin

Cited by 12 publications

References 43 publications

Metathesis Reactions in Natural Product Fragments and Total Syntheses

Metathesis Reactions in Natural Product Fragments and Total Syntheses

Stereoselective Synthesis and Antiproliferative Activities of Tetrafunctional Diterpene Steviol Derivatives

Gold(I)-Catalyzed Benzylic C(sp3)-H Functionalizations: Product Bifurcation towards Indole[a]- and [b]-Fused Polycycles

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