1-Decanol synthesis

The synthesis of the amino alcohol (5S,6S)-6-amino-5-decanol begins with reaction of the 1-chloropentylboronic ester (Section 1.1.2.1.3.1.) with sodium azide under phase-transfer conditions to form the a-azido boronic ester, which yields the a-chloro- -azidoalkyl boronic ester (1) [yield 92 % 95 % de] with (dichloromethyl)lithium under the usual conditions. The reaction of 1 with butylmagnesium chloride is unusual in that it requires zinc chloride in order to accomplish the replacement of chlorine by butyl to form /J-azidoalkyl boronic ester 2 without boron-azide /1-elimination. Standard peroxidic deboronation and reduction of the azide complete the synthesis15. 

Silica Gels. The acid-catalyzed alkoxide sol-gel process produces gels (17). Frib-erg and coworkers (40-50) pioneered the extension of this process to silica synthesis in microemulsions both aqueous and nonaqueous microemulsions were used. For aqueous microemulsions, experiments were conducted mostly with the SDS/ pentanol/water/acid system. A representative flow diagram is shown in Figure 2.2.9. The nonaqueous microemulsion systems utilized included CTAB/decanol/ decane/formamide and AOT/decane/glycerol (44-46,49,50). The experimental approach followed the sequence nonaqueous microemulsion preparation, water addition, and then TEOS addition. 

The structure of the western corn rootworm sex pheromone is 8-methyl-2-decanol propanoate (] 6) and four stereoisomers are possible (Figure 7). In our synthesis (3), we coupled a chiral 5-carbon unit to a 6-carbon fragment that had the requisite substitution to allow resolution at the oxygenated carbon. As mentioned earlier, (S)-2-methylbutyric acid was available to us from the alcohol. D-Isoleucine served as a source for the (R)-acid. Nitrosation, followed by decarboxylative oxidation of the intermediate hydroxyacid led to the (R)-2-methylbutyric acid in 96% ee. The process of fractional crystallization was... 

For the synthesis of sulfobacin A (158) and flavocristamide A (160), TBS ether of (f )-3-hydroxy-15-methylhexadecanoic acid was necessary, which was synthesized from 10-bromo-l -decanol (A) as shown in Figure 6.20. Chain elongation of A under the Schlosser conditions gave B, which was oxidized with PCC to give aldehyde C. ( )- 3-Hydroxy ester D was prepared from C by treatment with ethyl acetate and LDA. The corresponding ( )-acid was acetylated with vinyl acetate in the presence of lipase PS to give enantiomerically pure (R)-hydroxy acid and the acetylated (S )-acid. The former was converted to its TBS ether E. 

The tricyclo[4.3.1.03,7]decanol 38, an intermediate in the synthesis of ( )-9-isocyanop-upukeanane (39, isolated from the nudibranch Phyllidia varicasa and from its prey, a sponge, Hymeniacidon sp.) is synthesized by stereocontrolled addition of isopropenylmagnesium bromide to norbornenone derivative 34 and anionic oxy-Cope rearrangement of diol 35 as the key steps 1067. 

Studies of the sex pheromone of the Douglas fir tussock moth required the synthesis of ( )-l,6-henicosadien-ll-one. Outline a synthesis of this ketone using (Q-5,10-undecadien-l-ol and 1-decanol as sources of all of the carbons. 

In a later work [222], a unique three-microemulsion system was put to use for synthesis. The reverse micellar solution had DODMAC (surfactant) and 1-decanol (co-surfactant) in isooctane. DODMAC (= dioctyldimethylammonium chloride) was added via Bardac-LF-80 containing about 80% DODMAC in ethanol/water... 

Tsuji reported a total synthesis of zearalenone using Pd-catalyzed carbonylation. In this total synthesis, they synthesized the key compound by Pd-catalyzed carbonylation. The reacion of l-iodo-2-phenylthiomethyl-4,6-dimethoxybenzene 3 (Scheme 7) with 10-iodo-6,2 -[l,3]dioxolane-2-decanol 4 was carried out under carbon monoxide (12 atm) to afford the corresponding m-iodoalkyl ester of 2-phenylthiomethy 1-4,6-dimethoxybenzene 5. 

The requirements for the design of alkyl polyglycoside production plants based on the Fischer synthesis are critically determined by the carbohydrate types used and by the chain length of the alcohol used as described here for the production of alkyl polyglycosides on the basis of octanol/decanol and dodecanol/tetradecanol. 

Thus, starting from ethyl (5)-p-hydroxybut5rrate, pheromones of diverse structural types, such as (5)-sulcatol [26], femilactone II [27], (25,6i )-2-methyl-l,7-dioxaspiro[5.6]-dodecane [28], (25,6/ ,S5)-2,8-dimethyl-l,7-dioxaspiro[5.5]undecane [29], (2R,5S)-2-methyl-5-hexanolide [31], and (2S,SjR)-8-methyl-2-decanol propanoate [32], have been synthesized. Methyl (5)-P-hydroxybutyrate has also been used for the synthesis of (25,35,75)-3,7-dimethylpentadecan-2-ol [33]. In these syntheses, the configurations at the... 

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