Achillea amide

The Achillea amide 141 and related Othantus maritimus amide 142 were recently synthesized as illustration of a general approach to dienamides. Beginning with (l ,3 )-4-tn-n-butylstannyl-1-trimethylsilyl-1,3-butadiene, each terminal group was selectively substituted with the appropriate electrophilic reagent [422]. 

Pellitorine (1) has been isolated from several plants fruits of Piper sarmentosum [7], roots of Anacyclus pyrethrum [8] and seeds of Piper sylvaticum and presents insecticidal activity [10]. The Z-isomer (2), isolated from Piper guineense [11], has similar activity. Another component of the dried fruits of Piper sarmentosum, known in Thailand as Cha-plu , is sarmentine (3) which is used as an expectorant [7]. The corresponding piperidine derivative (4) is an Achillea amide [12]. 

A related strategy starts from 8-tosyldienamides easily prepared by iodosulfonylation of (2 )-pentadienamides. The latter reagents react as 8-acyldienyl cations [54] with Grignard reagents and give sarmentine (3) and Achillea amide (4) stereoselectively (Scheme 11). 

Isomerization reactions of 2-ynoic acids [59] and P-allenic amides [60] also provide suitable methodologies for the preparation of conjugated amides. The former compounds are isomerized by catalysis with ruthenium or iridium complexes and allow the synthesis of pellitorine (1), Achillea amide (4) and trichonine (13) (Scheme 15). 

The genus Achillea (Compositae) has provided a large variety of amides derived from long-chain unsaturated acids. Investigations by Bohlmann and coworkers led to the isolation of the following bases tetradeca-(2E, 6E, %E, 122)-tetraen-10-ynoic acid 2, 3 -dehydropyrrolideide (38) from A. tomentosa L. (77),... 

A new piperidine amide (150) was isolated from Achillea lingustica. Its structure was determined using UV, MS and NMR [417],... 

Seven new piperidine amides were isolated from Achillea species [418], Amides 143-147, and 149 were obtained from A. lycaonica, and 148, from A. chamaemelifolia. The structures of these compounds were determined using UV, IR, FDMS, EIMS, and H NMR [418]. 

New piperidine amide 154 was isolated from Achillea falcata, along with several known amides. Its structure was established using MS, UV, IR and and 13C NMR [419]. 13C NMR spectra were obtained, and H NMR-lanthanide induced shifts were determined for the amides [419],... 

A new piperideide (155) was isolated from Achillea millefolium, and its structure was determined using MS, UV, and H NMR [420]. Several previously known piperidine amides were also isolated from this plant, including the dominant 156. The stereochemistry of amides 157 and 158 was determined using the lanthanide induced shift method [420],... 

Five piperidine amides produced by Achillea (151-153,156,159) were tested as inhibitors of cyclooxygenase and 5-lipoxygenase, key enzymes in arachidonic acid metabolism. Each of the amides inhibited cyclooxygenase. Amides 152 and 153 inhibited 5-lipoxygenase, 156 and 159 were weak inhibitors of this enzyme, and 151 showed no inhibition. [421]. 

HPLC was used to separate and analyze amides in the Achillea millefolium group [423], and a number of known piperidine amides were isolated from Achillea ptarmica [424,425]. 

The roots of certain Achillea spp. contain several new amides, two of which are the pyrrolidides, (6) and (7) respectively, of... 

In the pepper alkaloid group, several new amides have been isolated from Achillea spp. One of them, from A, biebersteinil Afan, is the piperideide(19)Others include (20) (from A. ly caonica Boiss, et Heldr.), and the hitherto structurally unencountered acetylenic amides (21) and (22) (from A. spinulifolia Fenzl ex... 

The prevalence of isobutylamine, pyrrolidine and piperidine as the amine component of amides from numerous species of Piper has been noted, and is clearly evident in Tables 1 and 2. In a 1973 paper, Bohlmatm [14] speculated on the biosynthetic origins of the amine moieties of some amides belonging to the same class isolated from Achillea spp. (Compositae). He drew attention to the strong probability that the isobutylamine component, where present, would be derived from valine. He proposed, further, that the piperidine portion of the amide 10(n=4), and other piperidyl amides, is biosynthesized via pipecolic acid (now known to be most commonly derived from D-lysine [13]), and that lysine (configuration unspecified) is the progenitor of the piperideine ring embodied in 14 and 18 [14]. 

An interesting series of polyunsaturated amides (109-113) have been isolated from Achillea ptarmica (Compositae) (95). 

Isolation.- The cimides (84) - (86) occur in Leuooyolus formosus and (87) occurs in Achillea orithmifolia, The related acetylenic amides from A. tomentosa have already been described. The olefinic... 

Greger H, Zdero C, Bohlmann F (1987) Pyrrole amides from Achillea ageratifolia. Phytochemistry 26 2289-2291... 

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