Reaction of 2,4-decadienal with

In contrast to the reaction of 2-decenal with H2S a much more complex reaction mixture is obtained from the reaction of 2,4-decadienal with H2S in an aqueous medium at pH As 8... 

The fatty, tallowy-smelling aroma compound 2-pentylpyridin (56), which has been identified in roasted sesame seeds [77], is formed from the reaction of a fat oxidation product, 2,4-decadienal, with ammonia from the degradation of amino acids like glutamine and asparagine [78] (cf. Fig. 3.33). 

N-Heterocyclics. The reaction of primary amines with the carbonyl products derived from lipid oxidation is a major pathway in lipid-protein interactions. Formation of Schiff s base intermediates followed by cyclization and rearrangement can yield imines, pyridines and pyrroles (5,15,30,31). For example, 2-pentylpyridine may result from the reaction of ammonia with 2,4-decadienal, one of the principle aldehydes from the autoxidation of linoleate (5). 

Polyunsaturated aliphatic alkohols, aldehydes, ketones, and esters occur as fragrance components in fats, oils, fruits and plants 158). As an example the synthesis of ethyl (2 ,4Z)-2,4-decadienoate (232, pear ester ), which is responsible for the aroma of bartlett pears 161) is given. 2,4-Diunsaturated ester 232 may be obtained by a number of highly stereoselective syntheses, a lot of them making use of the Wittig reaction. Ohloff and Pawlak condensed 4,5-epoxy-( )-2-pentenal 228 with the ylide generated from 229 (butyllithium/ether) to the alkadiene epoxide 230 which was oxidized with periodic acid to the 2,4-decadienal 231. 231 is subsequently converted with MnOj/NaCN in ethanol to the pear ester 232162) [75 % (Z)-amount of the C-4 double bond] (Scheme 44). 

CIC the earthy odour of fresh potatoes is represented by 2-isopropyl-3-methoxy pyrazine. This earthy note is supported by the mushroom character of l-octen-3-ol. The key component of boiled potatoes is 3-(methylthio)-propanal, balanced with dimethyl sulphide. The high reaction temperatures in baked and fried potatoes start the Maillard reaction to form mainly heterocyclic components 2-ethyl-3,5-dimethyl pyrazine, 2-ethyl-6-vinyl pyrazine, 5-methyl-6,7-dihydro-(5H)cyclopenta-pyrazine, 2-acetyl-l,4,5,6-tetrahydro-pyridine are responsible for the roasted, nutty cracker-like flavour. The heat-induced degradation of the potato lipids and the frying oil imparts a fatty, tallowy character to the french fried potatoes. (E,E)-2,4-Decadienal, 2-octenal, octanoic acid and decanoic acid are main contributors to this fatty note. 

Brase and coworkers [29] also reported highly enantioselective desymmetrization of rran5-bicyclo[4.4.0]decadienes 81-84, which were prepared through Birch reduction of naphthalene, epoxidation and epoxide-opening reaction (Figure 13.11). The position of C=C double bonds also differed from the previous report [25], Although a Mizoroki-Heck reaction of aryl iodide 81 with the usual chiral ligands such as BINAP, DIOP i(2R,3R)- or (25,35)-0-isopropylidene-2,3-dihydroxy-l,4-bis(diphenylphosphino)butane)... 

Phospholipids contribute specific aroma to heated milk, meat and other cooked foods through lipid oxidation derived volatile compounds and interaction with Maillard reaction products. Most of the aroma significant volatiles from soybean lecithin are derived from lipid decomposition and Maillard reaction products including short-chain fatty acids, 2-heptanone, hexanal, and short-chain branched aldehydes formed by Strecker degradation (reactions of a-dicarbonyl compounds with amino acids). The most odor-active volatiles identified from aqueous dispersions of phosphatidylcholine and phos-phatidylethanolamine include fra 5 -4,5-epoxy-c/5-2-decenal, fran5,fran5-2,4-decadienal, hexanal, fra 5, d5, d5 -2,4,7-tridecatrienal (Table 11.9). Upon heating, these phospholipids produced cis- and franj-2-decenal and fra 5-2-undecenal. Besides fatty acid composition, other unknown factors apparently affect the formation of carbonyl compounds from heated phospholipids. 

If cyclopentene would react pair-wise with 2-pentene, only one product would form, namely 2,7-decadiene, and a similar result for cyclodimers etc. of cyclopentene. If somehow, the alkylidene species would be transferred one by one, we would obtain a mixture of 2,7-nonadiene, 2,7-decadiene, and 2,7-undecadiene in a 1 2 1 ratio. The latter turned out to be the case, which led the authors to propose the participation of metal-carbene (metal alkylidene) intermediates [6], Via these intermediates the alkylidene parts of the alkenes are transferred one by one to an alkene. The mechanism is depicted in Figure 16.4. In the first step the reaction of two alkylidene precursors (ethylidene -bottom- and propylidene -top) with cyclopentene is shown. In the second step the orientation of the next 2-pentene determines whether nonadiene, decadiene or undecadiene is formed. It is clear that this leads to a statistical mixture, all rates being exactly equal, which need not be the case. Sometimes the results are indeed not the statistical mixture as some combinations of metal carbene complex and reacting alkene may be preferred, but it is still believed that a metal-carbene mechanism is involved. Deuterium labelling of alkenes by Gmbbs instead of differently substituted alkenes led to the same result as the experiments with the use of 2-pentene [7],... 

Mori has reported the nickel-catalyzed cyclization/hydrosilylation of dienals to form protected alkenylcycloalk-anols." For example, reaction of 4-benzyloxymethyl-5,7-octadienal 48a and triethylsilane catalyzed by a 1 2 mixture of Ni(GOD)2 and PPhs in toluene at room temperature gave the silyloxycyclopentane 49a in 70% yield with exclusive formation of the m,//7 //i -diastereomer (Scheme 14). In a similar manner, the 6,8-nonadienal 48b underwent nickel-catalyzed reaction to form silyloxycyclohexane 49b in 71% yield with exclusive formation of the // /i ,// /i -diastereomer, and the 7,9-decadienal 48c underwent reaction to form silyloxycycloheptane 49c in 66% yield with undetermined stereochemistry (Scheme 14). On the basis of related stoichiometric experiments, Mori proposed a mechanism for the nickel-catalyzed cyclization/hydrosilylation of dienals involving initial insertion of the diene moiety into the Ni-H bond of a silylnickel hydride complex to form the (7r-allyl)nickel silyl complex li (Scheme 15). Intramolecular carbometallation followed by O-Si reductive elimination and H-Si oxidative addition would release the silyloxycycloalkane with regeneration of the active silylnickel hydride catalyst. 

Metallacyclobutane species (which then afford initiating carbenoids) can be formed in polymerisation systems with supported catalysts by monomer reaction via a metal re-allyl complex and metal hydride. A reaction of this type, where the olefin is 2,8-decadiene, is shown by the following scheme (R = H3CCH=CH-(CH2)4-) [116] ... 

Based on a similar approach, Backvall403 established the stereochemical course of such reactions and developed efficient routes to bicyclo[4.3.0]-nonadiene and bicyclo[5.3.0]-decadiene systems. Backvall404 has also reported a Pd(02CCF3)2-catalyzed oxidative carbocyclization of allenenes (Scheme 125). The process is efficient even with catalyst loading as low as 1 mol%, although if requires/>-benzoquinone as the stoichiometric oxidant, which represents the first example of a C-C bond formation using a catalytic amount of Pd(ll). Bicyclic adducts have been obtained in... 

---