Pheromone chemoenzymatic synthesis

Mori K (2000) Chemoenzymatic synthesis of pheromones, terpenes, and other bioregulators. In Patel RN (ed) Stereoselective biocatalysis. Marcel Dekker, New York, p 59... 

Scheme 23 Chemoenzymatic synthesis of the (3S,4R)-enantiomer of the lactol pheromone of Biprorulus bibax [112]...

Kalaitzakis, D., Rozzell, J.D., Kambourakis, S. and Smonou, I., A two-step chemoenzymatic synthesis of the natural pheromone (+)-Sitophilure utilizing isolated, NADPH-dependent ketoreductases. Eur. J. Org. Chem., 2006, 2309-2313. 

Complementary, inverse approaches for the FruA-based chemoenzymatic synthesis of the insect pheromone (+)-e)ro-brevicomin. 

The same enzymes were also applied to the DKR of a-alkyl-P-keto esters, such as 20, 21, 43, and 44, for the preparation of the corresponding hydroxy esters with excellent chemical and optical purity, as shown in Scheme 12.22 [55a,57j. In this case, substrate 43 was selected for the asymmetric chemoenzymatic synthesis of the aggregation pheromone 45 (sitophilate) of the granary weevil Sitophilus granarius (Scheme 12.23) [57]. 

Scheme 12.23 Chemoenzymatic synthesis of sitophilate - a natural pheromone.

Lebreton J, Alphand V, Furstoss R. Chemoenzymatic synthesis of marine brown algae pheromones. Tetrahedron 1997 53 145-160. 

Chemoenzymatic Synthesis of Pheromones, Terpenes, and Other Bioregulators... 

This decarboxylation reaction serves as the tool for enzyme-mediated organic synthesis [136,137]. As seen in Eq. (27), the addition of thiazolium intermediate derived from hy-droxypyruvate proceeds via re face attack to afford the products (76) with stereochemically defined 2,3-erythro stereochemistry. The examples are summarized in Table 7. This method works very well for the synthesis of naturally occurring phosphorylated [126,134], nonphosphorylated ketoses [120,125], and deoxy sugars [115,124]. Moreover, 2,3-erythro-dio motif is exemplified in the chemoenzymatic synthesis of die L-series of aldoses (77-79) [122], aza sugars (80,81) [128-130] and ( )-gjco-brevicomin (69), an insect pheromone [131] (Tab e 8). The stereochemically controlled syntiiesis of aldehydes with d(2) config-... 

Archelas A, R Furstoss (1992) Synthesis of optically pure pityol—a pheromone of the bark beetle Pityophtho-rus pityographus—using a chemoenzymatic route. Tetrahedron Lett 33 5241-5242. 

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