Synthesis and NMR characterisation of novel highly cyclised polyprenoid hydrocarbons from sediments

Grosjean, Emmanuelle; Poinsot, Jacques; Charrié-Duhaut, Armelle; Tabuteau, Stéphanie; Adam, Pierre; Trendel, Jean M.; Schaeffer, Philippe; Connan, Jacques; Dessort, Daniel; Albrecht, Pierre

doi:10.1039/b008104n

Cited by 9 publications

(1 citation statement)

References 27 publications

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“…The current method requires functionalization at the head of the isoprenoid skeleton. For this purpose ( E , E )-farnesol ( S3 ) was acetylated and then subjected to stereoselective allylic oxidation , at the terminal methyl group. The oxidation using 10 mol % of SeO 2 and 3.6 equiv of t -BuO 2 H in the presence of 10 mol % of salicylic acid followed by reduction with NaBH 4 gave allylic alcohol 7 in 29% yield.…”

Section: Results and Discussionmentioning

confidence: 99%

Convergent Synthesis of Menaquinone-7 (MK-7)

Baj

Wałejko

Kutner

et al. 2016

Org. Process Res. Dev.

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A practical synthesis of menaquinone-7 (MK-7, vitamin K2) in the all-trans form was designed. Stereoselective synthesis of MK-7 was achieved through a “1 + 6” convergent strategy by condensation of two building blocks, menadione monoprenyl derivative (fragment “1”) with hexaprenyl bromide (fragment “6”, 82%). Pd-catalyzed desulfonation with LiEt3BH (78%) was followed by oxidation of the hydroquinone moiety using ammonium cerium(IV) nitrate (72%). The major challenge in our methodology was the preparation of all-trans hexaprenyl bromide by coupling of two triprenyl units derived from trans,trans-farnesol. Manufacturing on a pilot scale was accomplished through our approach. The scalable method was designed especially for a large, kilogram-scale production from easily available intermediates. Furthermore, the proposed methodology avoids many chromatographic purifications and allows for a relatively cost-effective manufacturing. Moreover, our synthesis yielded high-purity (99.9%) final product MK-7, which can be used as a dietary supplement as well as an active pharmaceutical ingredient.

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Section: Results and Discussionmentioning

confidence: 99%

Convergent Synthesis of Menaquinone-7 (MK-7)

Baj

Wałejko

Kutner

et al. 2016

Org. Process Res. Dev.

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ChemInform Abstract: Synthesis and NMR Characterization of Novel Highly Cyclized Polyprenoid Hydrocarbons from Sediments.

Grosjean¹,

Poinsot²,

Charrié-Duhaut³

et al. 2001

ChemInform

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Superacid‐Catalyzed Cyclization of Methyl (6Z)‐Geranylfarnesoates

Grinco

Kulciţki

Ungur

et al. 2007

Helvetica Chimica Acta

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Methyl (2Z,6Z,10E,14E)-(3) and methyl (2E,6Z,10E,14E)-geranylfarnesoate (4) were prepared, and then individually cyclized in the presence of the superacid FSO 3 H. In the case of substrate 3, the scalaranic ester 9 (26%) and the cheilanthanic ester 10 (39%) were isolated. Under the same conditions, substrate 4 afforded a mixture of the corresponding stereoisomers 11 (25%) and 12 (63%). The observed product selectivity supports that the internal, (6Z)-configured C¼C bond in these and other biologically relevant substrates plays an essential role in the cyclization process.Introduction. -Prenols represent a large class of natural, linear isoprenoids that occur abundantly in plant kingdom. Their diversity is due to the (E/Z)-configuration of the C¼C bonds and their chain length, which may vary from two (in monoterpenols) to several thousand (in natural rubber) isoprene units [1]. Terpenols with short chain lengths (up to five isoprene units) having all their C¼C bonds in (E)-configuration are regarded as biogenetic precursors of the corresponding cyclic isoprenoids. Based on this notion, many biomimetic syntheses of cyclic terpenoids have been elaborated, which turned out to serve not only as demonstrations of the biogenetic origin of cyclic isoprenoids, but also as very efficient synthetic tool for their in vitro preparation. Superacid-catalyzed cyclization of regular-structured, short-chain terpenoids is one of the most-successful biomimetic procedures to establish a link between the cyclic compounds and their aliphatic precursors [2].Biomimetic cyclization of long-chain polyprenols has also been investigated, and successful attempts of both enzymatic [3] and superacidic [4] cyclization have been reported; but only prenols with (all-E)-configuration have been used as substrates. On the other hand, it is known that most of the natural long-chain polyprenols possess the so-called di-trans-poly-cis or tri-trans-poly-cis configuration 1 ). To the best of our knowledge, none of these compounds have been used as substrates for biomimetic cyclizations.We have shown in recent papers [5] [6] that the presence of an internal (13Z)-configured C¼C bond in the bicyclic, stereoisomeric compounds methyl (13Z,17Z)-(1) and methyl (13Z,17E)-bicyclogeranylfarnesoate (2) influences the selectivity of the

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Synthesis and NMR characterisation of novel highly cyclised polyprenoid hydrocarbons from sediments

Cited by 9 publications

References 27 publications

Convergent Synthesis of Menaquinone-7 (MK-7)

Convergent Synthesis of Menaquinone-7 (MK-7)

ChemInform Abstract: Synthesis and NMR Characterization of Novel Highly Cyclized Polyprenoid Hydrocarbons from Sediments.

Superacid‐Catalyzed Cyclization of Methyl (6Z)‐Geranylfarnesoates

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