Total synthesis of D-homodinordrin

The analysis of cuticular extracts from the kleptoparasitic spider Argyrodes elevatus revealed the presence of unusual esters, new for arthropods. These novel compounds proved to be methyl-branched long-chain fatty acid esters with methyl branches located either close or remote from the internally located ester group. The GC/MS analysis of the prosoma lipid blend from the male cuticle contained one major component, undecyl 2-methyltridecanoate (1). In contrast, four major wax-type esters, 2-methylundecyl 2,8-dimethylundecanoate (2), 2,8-dimethylundecyl 2,8-dimethylundecanoate (3), heptadecyl 4-methylheptanoate (4), and 14-methylheptadecyl 4-methylheptanoate (5), were identified in the lipid blend of female prosomata. Structure assignments were based on mass spectra, gas chromatographic retention indices, and microderivatization. Unambiguous proof of postulated structures was ensured by an independent synthesis of all five esters. Preferentially, odd-numbered carbon chains pointed to a distinct biosynthetic pathway, different from that of common fatty acids, because one or two C starter units are incorporated during the biosynthesis of all acid and alcohol building blocks present in the five esters. The striking sexual dimorphism together with the unique biosynthesis points to a function of the esters in chemical communication of the spiders, although no behavioral data are currently available to test this assumption.

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“…of aq. LiOH was added and the mixture was allowed to stir overnight at r.t. [53]. The reaction was controlled with TLC.…”

Section: Hydrolysis Using Lithium Hydroxidementioning

confidence: 99%

Identification and Synthesis of Branched Wax‐type Esters, Novel Surface Lipids from the Spider Argyrodes elevatus (Araneae: Theridiidae)

Chinta

Goller

Uhl³

et al. 2016

Chemistry & Biodiversity

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“…The McMurry reaction has also been used in the last few years to form macrocylic alkenes in the cases of cyclic diterpenes sarcophytols A and B [11] and epoxydihydrocembrenes C [12] (Scheme 3). The double bond is formed very (E)-Alkene units are frequently found in macrocyclic natural products.…”

Section: Doyle Et Al Reported the Synthesis Of Patulolides A And B Bmentioning

confidence: 99%

“…Catalysts for ring-closing metathesis (RCM). Synthesis of recifeiolide(12). Influence of the temperature on the selectivity of the RCM.…”

mentioning

confidence: 99%

Recent Methods for the Synthesis of (E)‐Alkene Units in Macrocyclic Natural Products

Prunet

2003

Angew Chem Int Ed

167

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(E)-Alkene units are frequently found in macrocyclic natural products. Among the reactions that form the double bond during the cyclization, the classical Horner-Emmons coupling is still frequently used with success. During the last decade, ring-closing metathesis has emerged as a very powerful tool for the synthesis of large rings, but the E/Z selectivity, which is rarely predictable, depends on many factors which will be discussed in this review. The best solution might be a two-step procedure involving ring-closing alkyne metathesis (RCAM) followed by stereoselective reduction of the macrocyclic alkyne unit to the corresponding E double bond.

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“…[4][5][6] It was found that the presence of 4-(dimethylamino) pyridine (DMAP) will substantially increase the rate of the reaction. [7] The acylation of alcohols, phenols, and amines is catalyzed with a variety of catalysts such as cobalt chloride (CoCl 2 ), [8] Sc(OTf ) 3, [9] TaCl 5, [10] montmorillonite K10, [11] HY zeolite, [12] In(OTf ) 3, [13] Cu(OTf ) 2, [14] silica gel-supported sulfuric acid, [15,16] yittria/zirconia-based Lewis acid, [17] InCl 3 /Mont. K 10, [18] sodium dodecyl sulfate (SDS), [19] ammonium acetate in acetic acid, [20] manganese (III) bis(2-hydroxyanil)acetylacetonato complex, [21] silica sulfate, [22] p-MeC 6 H 4 SO 2 NBr 2, [23] DBDMH or TCCA, [24] ZnCl 2, [25] H 6 P 2 W 18 O 62 Á 24H 2 O, [26] vanadyl sulfate, [27] La(NO 3 ) 3 Á 6H 2 O, [28] 2,4,6-triacyloxyl,3,5-triazine (TAT), [29] zinc dust, [30] ionic liquid based on morpholin, [31] borated zirconia, [32] DMAP-saccharin, [33] copper-catalyzed azidation reaction of anilines(primary amine), [34] acylation of phenol and salicylic acid in the presence of zirconium phosphate (ZP) nanoparticles, [35] oxidative acylation of phenols with N-heteroarylmethanes under transition metals, [36] N-alkylation of amines with alcohols in presence of PNP manganese pincer complexes, [37] trifluoromethanesulfonic acid (TfOH)-catalyzed acylation of phenol and its derivaties, [38] bacterial acyltransferase acylation of phenolic compounds, [39] and acylation of BN-arenes using BNarene and acyl chloride in order to synth...…”

Section: Introductionmentioning

confidence: 99%

Werner transition‐metal complex (WTMC)‐mediated mild and efficient chemo‐selective acylation of phenols and anilines under solvent‐free condition

Sarief

Haque

Feroze

et al. 2018

J Chinese Chemical Soc

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Werner‐type transition‐metal complexes (WTMC) such as [Co(NH3)5Cl]Cl2, Cu[(NH3)4]SO4, Mn(acac)3, Ni[(NH3)6]Cl2, Ni[(en)3]S2O3, and Hg[Co(SCN)4] efficiently promote the chemoselective acetylation of phenols and anilines under solvent‐free condition. The results of this study clearly shows that the optimal condition for the acetylation of anilines/phenols (1 mmol) (2a–r) with acetic anhydride (1.2 mmol) in the presence of WTMC (1 mmol) and two drops of H3PO4 on heating for 10 min under solvent‐free condition gives the corresponding acetanilides/phenyl acetate (3a–r) in good to excellent yield. Furthermore, the method is simple, efficient, chemoselective, and eco‐friendly under solvent‐free condition for the acetylation of anilines and phenols promoted by WTMC by using acetic anhydrate as the acetylating agent. The simple preparation of the catalyst, easy procedure of the acetylation reaction, and simple work‐up indicate the importance of WTMC for such reactions.

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Total synthesis of D-homodinordrin

Cited by 11 publications

References 4 publications

Identification and Synthesis of Branched Wax‐type Esters, Novel Surface Lipids from the Spider Argyrodes elevatus (Araneae: Theridiidae)

Identification and Synthesis of Branched Wax‐type Esters, Novel Surface Lipids from the Spider Argyrodes elevatus (Araneae: Theridiidae)

Recent Methods for the Synthesis of (E)‐Alkene Units in Macrocyclic Natural Products

Werner transition‐metal complex (WTMC)‐mediated mild and efficient chemo‐selective acylation of phenols and anilines under solvent‐free condition

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