Royal jelly acid,

The telomer 137, obtained by the reaction of butadiene with malonate, is a suitable compound for the syntheses of naturally occurring dodecanoic acid derivatives, such as queen substance (I38)[l 7], one of the royal jelly acids (139)[I18], and pellitorine fl40)[ll9]. 

The 3.8-nonadienoate 91, obtained by dimerization-carbonylation, has been converted into several natural products. The synthesis of brevicomin is described in Chapter 3, Section 2.3. Another royal jelly acid [2-decenedioic acid (149)] was prepared by cobalt carbonyl-catalyzed carbonylation of the terminal double bond, followed by isomerization of the double bond to the conjugated position to afford 149[122], Hexadecane-2,15-dione (150) can be prepared by Pd-catalyzed oxidation of the terminal double bond, hydrogenation of the internal double bond, and coupling by Kolbe electrolysis. Aldol condensation mediated by an organoaluminum reagent gave the unsaturated cyclic ketone 151 in 65% yield. Finally, the reduction of 151 afforded muscone (152)[123]. n-Octanol is produced commercially as described beforc[32]. 

One of royal jelly acids (10-hydroxy-2-decenoic acid) (141) was prepared from the telomer of acetoacetate, 142 (128). The terminal double bond was converted to terminal alcohol by hydroboration. The internal double bond was reduced and then reintroduced at the conjugated position by the addition of phenylselenyl group, and its oxidative removal completed the synthesis ... 

Nonadienoate (73) is used for the synthesis of another royal jelly acid, 2-decenedioic acid (146) (130). The terminal double bond was car-bonylated with Co2(CO)8 coordinated by pyridine. Linear ester was obtained in 80% selectivity. Hydrolysis and double-bond migration promoted by strong base produced royal jelly acid (146) as a crystalline compound. 

Natural Products.—The use of 2-oxoalkylphosphonates still appears to be the method of choice for the preparation of the C8-side-chain of prostaglandins. Examples reported this year were in the preparation of azaprostaglandins,119 aryl analogues,120 and the analogue (131),121 among others. Royal jelly acid has been... 

Selenoxide elimination.3 A short synthesis of royal jelly acid (2) from a commercially available starting material (1) involves phenylselenenylalion followed by concurrent ozonation of a double bond and selenoxide elimination (equation I). 

Carbonylation of butadiene in alcohol catalyzed by Pd(OAc)2/PPli3 affords 3,8-nonadienoate 142 in high yield52, 53. The synthesis of 2-decenedioic acid (144) (royal jelly acid) may be carried out as follows54 Carbonylation of 142 in alcohol... 

Royal jelly acid, C10H 8Oj, tram-1 0-hydroxy-A2-decenoic acid. HCKCHjJjCH —CHCOOH. Constitutes about 10% of the dried royal jelly. Isoln Townsend, Lucas, Biochem. J. 34, 1155 0940) Butenandt, Rembold, Z. Physiol. Chem. 308, 284 (1957). Synthesis Fray el al. Tetrahedron Letters 4, 15 (1960) Smissman et al, J. Org. Chem. 29, 3517 (1964k Bestmann et al, Ann. 699, 33 (1966) J. Tsuji et al. Bull Chem. Soc. Japan SO, 2507 (1977) T. Fujisawa et al. Chem. Letters 1982, 219 R. Chiron, J. Chem. Ecol 8, 709 (1982). Prevention of leukemia in mice with royal jelly acid Town -send et al,. Nature 183, 1270 (1959). Prisms from ether + petr ether or methanol + water, mp 64-65. nv max 211... 

Zur Herstellung von, Royal jelly acid" und Queen substance" iiber Malonsaure-diester und 3-Oxo-butansaure-ester-Synthesen s. K. Yokoiu. K Matsubara, Nippon Kagaku Kaishi 1978,1415 C. A. 90, 22266 (1979). 

Generally the conditions required to carry out the Horner-Wittig reaction are not compatible with sensitive functional groups such as hydroxy-, nitro-, and keto-aldehydes these residues must normally be protected. However, the use of a heterogeneous base such as K CO in either aqueous or organic media allows the condensation of these sensitive substrates with activated phosphorates to take place directly. The synthesis of Royal Jelly acid from 8-... 

Example (see also [44,51,52]). Synthesis of royal jelly acids ... 

Zakharkin published the stereospecific synthesis oi 6E, llZ-hexadecadien-1-yl acetate, the Antheraca polyphemus pheromone, accomplished on the basis of either the malonate or the acetoacetate telomer [18]. The acetoacetate telomer is also the precursor of one of the royal jelly acids, the lO-hydroxy-2-decenoic acid (Equation 17) [19]. 

For instance, with aliphatic alcohols the alkyl nona-3,8-dienoates are formed [25, 26], This nonadienoate can be used for the synthesis of another royal jelly acid, the 2-decenedioic acid (Equation 22). Carbonyla-tion of the nonadienoate in alcohol using Co2(CO)g/pyridine as the catalyst yields a linear diester which can be transformed into the royal jelly acid by hydrolysis and concomitant double bond migration [27]. 

The chemistry of royal jelly has been extensively studied. Chemical constituents reported to be present hydroxy fatty acids, including 10-hydroxy-fra j -2-decenoic acid (royal jelly acid 10-HDA), which ranges between 1.64% and 4.24% (usually 2.0-2.5%) in fresh royal jelly and up to 7.0% in the freeze-dried product (usual range 4.5-5.5%), 10-hydro-xydecanoic acid (0.60-1.25%) " 10-acet-oxydecanoic acid, 11-S-hydroxydodecanoic acid, hydroxy-2 -decenoic acid 10-phosphate, and others gluconic acid, sebacic acid and 2-decenedioic acid, /)-hydroxyben-zoic acid, 3-hydroxydecanoic, 8-hydroxyde-canoic, and 3,10-dihydroxydecanoic acids ° sterols including methylenecholesterol (ca. 

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