Synthesis of two piperidine alkaloids, (−)-deoxoprosopinine and (−)-deoxoprosophylline, from 6-hydroxylated dihydrosphingosine derivatives

Fuhshuku, Ken‐ichi; Mori, Kenji

doi:10.1016/j.tetasy.2007.08.028

Cited by 20 publications

(5 citation statements)

References 21 publications

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“…This is reflected in the stereochemistry of cyclized products 27 and 30 . The spectroscopic data of synthesized compounds 10 and 11 were in absolute agreement with the reported data 19,20…”

Section: Resultssupporting

confidence: 87%

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A Concise Synthesis of (2R,3R)‐ and (2R,3S)‐3‐Hydroxypipecolic Acids, and Total Synthesis of (–)‐Deoxoprosopinine and (+)‐2‐epi‐Deoxoprosopinine from D‐Glycals

Mallick¹,

Kumari²,

Roy³

et al. 2014

Eur J Org Chem

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“…This is reflected in the stereochemistry of cyclized products 27 and 30 . The spectroscopic data of synthesized compounds 10 and 11 were in absolute agreement with the reported data 19,20…”

Section: Resultssupporting

confidence: 87%

“…The solution was concentrated in vacuo to give compound 10 (87 mg, 87 %) as a solid, m.p. 88–90 °C (CHCl 3 ) [ref 19. m.p.…”

Section: Methodsmentioning

confidence: 99%

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A Concise Synthesis of (2R,3R)‐ and (2R,3S)‐3‐Hydroxypipecolic Acids, and Total Synthesis of (–)‐Deoxoprosopinine and (+)‐2‐epi‐Deoxoprosopinine from D‐Glycals

Mallick¹,

Kumari²,

Roy³

et al. 2014

Eur J Org Chem

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“…Intramolecular displacement of a mesylate group by a Boc-protected amine (Scheme 13) was the key step for the synthesis of ( )-Deoxoprosopinine (84) reported by Mori [23]. The synthetic sequence started from (S)-Garner's aldehyde (85) which in 6 steps was elaborated to mesylate 86.…”

Section: Nucleophilic Substitutionmentioning

confidence: 99%

Stereoselective Syntheses of 2,6-disubstituted Piperidin-3-oles (alkaloid lipids)

Koulocheri¹,

Pitsinos²,

Haroutounian

2008

COC

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Alkaloid lipids comprise a class of natural compounds with significant biological activities of medicinal interest. Their structural framework consists of a 2,6-disubstituted-3-piperidinol moiety (polar head group) and a lipid tail. Representative examples of alkaloid lipids are (+)-Cassine, ( )-Prosophylline, ( )-Prosopinine, ( )-Spectalline.Many synthetic strategies have been developed for the efficient stereoselective synthesis of various natural alkaloid lipids and their synthetic analogues. This mini-review focuses on the most successful approaches published during the new millennium. The synthetic strategies are grouped in two main sections, depending on whether the lipophilic side chain is introduced before ("early") or after ("late") piperidine ring formation. These sections are further organised based on the key ring forming reaction/strategy employed.For the strategies that opt to introduce the lipophilic side chain early on the synthetic sequence, the intramolecular reductive amination, either with or without isolation of the intermediate imine/enamine, constitutes one of the most popular methods for constructing the piperidine ring followed closely by approaches based on the intramolecular alkylation of suitable amine derivatives. Olefin ring closing metathesis and intramolecular hetero-Diels-Alder reactions have also been exploited to secure the azaheterocycle.The intramolecular alkylation of an amine or the, retrosynthetically related, intramolecular amine addition to an olefin have also been employed as key ring-forming reactions by syntheses that adopt the more convergent approach of introducing the side chain on a preformed heterocycle. In this regard the introduction of the side chain via alkylation of pyridinium salts, alkylation of a lactam (2-piperidone) or glutarimide derivatives have been investigated. Several groups have also exploited the oxidative cyclization of -furylamines to prepare 2-dihydropyridones as a convenient scaffold for the late introduction of the lipid tail.In some cases, carbohydrates and aminoacids were used (either as starting materials or as chiral auxiliaries) for the enantioselective synthesis of alkaloid lipids. Enzymatic or chemical (Jacobsen's epoxide hydrolysis protocol) resolutions of racemic starting materials and Sharpless asymmetric epoxidation, dihydroxylation or aminohydroxylation of olefins have also been utilized.Finally, it is noteworthy that in several cases, apart from the Witting reaction and the use of Grignard reagents, olefin cross-metathesis has also been successfully employed for the introduction of the lipid side chain.

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“…6 To improve the cytokine production activity and selectivity, various derivatives of KRN7000 have been synthesized. [33][34][35][36][37] Notably, modifications of the alkyl chains in the sphingosine and fatty acyl moieties significantly influenced the balance of Th1/Th2 cytokine production. Truncation of the acyl chain (C8) leads to higher Th2 selectivity compared to full-length KRN7000.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Th1-immunostimulatory activity of α-galactosylceramide analogues bearing a halogen-containing or selenium-containing acyl chain

Hossain

Hanashima

Nomura

et al. 2016

Bioorganic & Medicinal Chemistry

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A novel series of CD1d ligand α-galactosylceramides (α-GalCers) were synthesized by incorporation of the heavy atoms Br and Se in the acyl chain backbone of α-galactosyl-N-cerotoylphytosphingosine. The synthetic analogues are potent CD1d ligands and stimulate mouse invariant natural killer T (iNKT) cells to selectively enhance Th1 cytokine production. These synthetic analogues would be efficient X-ray crystallographic probes to disclose precise atomic positions of alkyl carbons and lipid-protein interactions in KRN7000/CD1d complexes.

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Synthesis of two piperidine alkaloids, (−)-deoxoprosopinine and (−)-deoxoprosophylline, from 6-hydroxylated dihydrosphingosine derivatives

Cited by 20 publications

References 21 publications

A Concise Synthesis of (2R,3R)‐ and (2R,3S)‐3‐Hydroxypipecolic Acids, and Total Synthesis of (–)‐Deoxoprosopinine and (+)‐2‐epi‐Deoxoprosopinine from D‐Glycals

A Concise Synthesis of (2R,3R)‐ and (2R,3S)‐3‐Hydroxypipecolic Acids, and Total Synthesis of (–)‐Deoxoprosopinine and (+)‐2‐epi‐Deoxoprosopinine from D‐Glycals

Stereoselective Syntheses of 2,6-disubstituted Piperidin-3-oles (alkaloid lipids)

Synthesis and Th1-immunostimulatory activity of α-galactosylceramide analogues bearing a halogen-containing or selenium-containing acyl chain

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