Divergent total synthesis of penaresidin B and its straight side chain analogue

Fujiwara, Tomoya; Hashimoto, Kazuki; Umeda, Masanori; Murayama, Shotaro; Ohno, Yuki; Liu, Bo; Nambu, Hisanori; Yakura, Takayuki

doi:10.1016/j.tet.2018.07.023

Cited by 16 publications

(16 citation statements)

References 27 publications

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“…Yakura and co-workers presented the total synthesis of penaresidin B 727 (Scheme 112), a sphingosine consist of a 2,3,4-trisubstituted azetidine ring linked to an alkyl side chain with one chiral center, extracted from Okinawan marine sponge Penaressp, possess actomyosin ATPase-activating activity. [293] In this synthetic approach, the CM was one of the key transformations and was employed to couple the main fragments. The S N 2-type cyclization of mesylate 722 with NaH produced an allylazetidine 723, which was then converted to hydroxyazetidine 724 by removal of PMB-group with DDQ.…”

Section: Total Synthesis Of Natural Products Based On CMmentioning

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: Total Synthesis Of Natural Products Based On CMmentioning

confidence: 99%

Metathesis Reactions in Natural Product Fragments and Total Syntheses

et al. 2022

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“… Penaresidin B consists of a densely functionalized azetidine core with three contiguous stereocenters and a distally hydroxylated alkane side chain. Several total syntheses of penaresidin B − and related congeners − have been described, all relying on early stage nitrogen incorporation using starting materials such as Garner’s aldehyde and/or multistep functional group interconversions to construct the azetidine core. The shortest of the reported syntheses of penaresidin B is 17 linear steps .…”

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Intermolecular sp³-C–H Amination for the Synthesis of Saturated Azacycles

2019

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The preparation of substituted azetidines and larger ring, nitrogen-containing saturated heterocycles is enabled through efficient and selective intermolecular sp 3 -C−H amination of alkyl bromide derivatives. A range of substrates are demonstrated to undergo C−H amination and subsequent sulfamate alkylation in good to excellent yield. N-Phenoxysulfonylprotected products can be unmasked under neutral or mild basic conditions to yield the corresponding cyclic secondary amines. The preparative convenience of this protocol is demonstrated through gram-scale and telescoped multistep procedures. Application of this technology is highlighted in a nine-step total synthesis of an unusual azetidine-containing natural product, penaresidin B.

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“…Chiral azetidine-2-carboxylic acid, the first known example of naturally occurring azetidines, [8] and their derivatives (potential products from reduction of 2-azetine-carboxylates) are structural units of several natural products [9] and the thrombin inhibitor melagatran [10] (Figure 1). Va rious methods have been used for their preparation, [11] but all of them are multistep syntheses from chiral reactants that provide access only to mono-or disubstituted azetidine-2-carboxylic acids and their derivatives.Herein, we report arobust methodology for the highly enantioselective synthesis of 2-azetine-carboxylates catalyzed by copper(I) with chiral sabox ligand and their stereoselective hydrogenation to form as ingle stereoisomer of tetrasubstituted azetidine-2-carboxylate derivatives (Scheme 1c).…”

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Synthesis of Chiral Tetrasubstituted Azetidines from Donor–Acceptor Azetines via Asymmetric Copper(I)‐Catalyzed Imido‐Ylide [3+1]‐Cycloaddition with Metallo‐Enolcarbenes

et al. 2019

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The all-cis stereoisomers of tetrasubstituted azetidine-2-carboxylic acids and derivatives that possess three chiral centers have been prepared in high yield and stereocontrol from silyl-protected Z-g-substituted enoldiazoacetates and imido-sulfur ylides by asymmetric [3+ +1]-cycloaddition using chiral sabox copper(I) catalysis followed by Pd/C catalytic hydrogenation. Hydrogenation of the chiral p-methoxybenzyl azetine-2-carboxylates occurs with both hydrogen addition to the C = Cbond and hydrogenolysis of the ester.

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Divergent total synthesis of penaresidin B and its straight side chain analogue

Cited by 16 publications

References 27 publications

Metathesis Reactions in Natural Product Fragments and Total Syntheses

Metathesis Reactions in Natural Product Fragments and Total Syntheses

Intermolecular sp³-C–H Amination for the Synthesis of Saturated Azacycles

Synthesis of Chiral Tetrasubstituted Azetidines from Donor–Acceptor Azetines via Asymmetric Copper(I)‐Catalyzed Imido‐Ylide [3+1]‐Cycloaddition with Metallo‐Enolcarbenes

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Divergent total synthesis of penaresidin B and its straight side chain analogue

Cited by 16 publications

References 27 publications

Metathesis Reactions in Natural Product Fragments and Total Syntheses

Metathesis Reactions in Natural Product Fragments and Total Syntheses

Intermolecular sp3-C–H Amination for the Synthesis of Saturated Azacycles

Synthesis of Chiral Tetrasubstituted Azetidines from Donor–Acceptor Azetines via Asymmetric Copper(I)‐Catalyzed Imido‐Ylide [3+1]‐Cycloaddition with Metallo‐Enolcarbenes

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Intermolecular sp³-C–H Amination for the Synthesis of Saturated Azacycles