Gibberellin synthesis from

A total synthesis of ( )-royleanone from 5,7,8-trimethoxy-l-tetralone (123) has been described.129 The tetralone was converted into the tricyclic ketone (124), which was in turn converted into 11,12,14-trimethoxypodocarpatriene (125). Demethyla-tion and oxidation afforded the quinone (126 R = H) which was alkylated to give royleanone (126 R = Pr ). Synthetic studies in the resin acid series have led130 to the preparation of the dicarboxylic acid (127) with a cis a/b ring junction. The preparation of some tetracyclic ketones as intermediates for gibberellin synthesis has been described.131 132 The key reaction involves photolysis of a diazoketone (128) to afford the tetracyclic system (129). In a synthesis of phyllocladene from abietic acid... 

The 1,4-dihydrobenzoic acids derived from reductive alkylation may undergo facile rearomatization with either loss of the carboxylic acid group or the alkyl group. The gibberellin synthesis intermediate (82), for example, was found to be especially labile, forming (83) simply on exposure to air." Oxidative decarboxylation may be deliberately achieved with lead tetraacetate or electrochemically." Loss of the 1-alkyl group is likely to be a problem when the alkyl moiety can form a reasonably stable free radical, since a chain reaction may then be sustained." ... 

The procedure was used successfully in the synthesis of gibberellin C from the dienone group (7).4 The ketone group at C8 was protected by ketalization, carboxylation was conducted by the Robinson-Cornforth method, the resulting acid esterified with diazomethane, and finally the diketo diester (8) was obtained after... 

Recently, EPTC has been shown to inhibit the conversion of acetate and pyruvate to acetyl-CoA. However, this cannot directly explain the inhibition of enf-kaurene synthesis from MVA. It seems likely that the thiocarbamate effect on gibberellin biosynthesis is a secondary target. This was the conclusion from a study with diallate, which inhibited enf-kaurene synthetase only at high concentrations. Gibberellins may have a role in... 

Pioneering work on the desulphonylation of jS-ketosulphones was carried out by Corey and Chaykovsky - . This reaction was part of a sequence which could be used in the synthesis of ketones, as shown in equation (53). The main thrust of this work was in the use of sulphoxides, but Corey did stress the merits of both sulphones and sulphonamides for different applications of this type of reaction. The method soon found application by Stetter and Hesse for the synthesis of 3-methyl-2,4-dioxa-adamantane , and by House and Larson in an ingenious synthesis of intermediates directed towards the gibberellin skeleton, and also for more standard applications . Other applications of the method have also been madealthough it does suffer from certain limitations in that further alkylation of an a-alkyl- -ketosulphone is a very sluggish, inefficient process. Kurth and O Brien have proposed an alternative, one-pot sequence of reactions (equation 54), carried out at — 78 to — 50°, with yields better than 50%. The major difference between the two routes is that the one-pot process uses the desulphonylation step to generate the enolate anion, whereas in the Corey-House procedure, the desulphonylation with aluminium amalgam is a separate, non-productive step. 

Takano et al. 69) exploited the asymmetric aldolization for the synthesis of more functionalized chiral products which possess units suitable for the construction of certain tetracyclic triterpenes, such as gibberellins and kaurenes. They described the enantioselective synthesis of the tricyclic enone (33) from the symmetric triketone (32) and its conversion into the gibbane framework. Again, (S)-proline was used as the catalyst. 

In the germination of cereal seeds, it was long known by brewers that if the embryo was excised (or dead) the endosperm would not be hydrolyzed and sugars would not be released. In 1960, Paleg showed that amylolytic activity in the embryo-less half could be fully restored in the presence of gibberellin. In other words, the substance that passed from the embryo to the endosperm (or rather, to the living cells of the aleurone layer that encloses the dead endosperm) induces there the synthesis of a-amylase which is responsible for hydrolysis of the stored starch reserves held in the endosperm. The extent to which the a-amylase was induced became another bioassay for gibberellin. 

Riboflavin is produced by Clostridium, Ascomycetes and Candida species. The yield can be as high as 5 g 1 1 after 7 days 60). Gibberella fujikuroi is utilized for the synthesis of gibberellins, a group of plant hormones used for plant growth promotion. Glucose, molasses, lipid (corn oil) are usually used as carbon sources. Vitamin B12 may also be synthesized from alcohols and hydrocarbons. 

Irradiation of the a -unsaturated ketone derived by manganese dioxide oxidation of methyl gibberellate, affords, in the solid state, a dimer in which addition of the unsaturated ketone across the terminal methylene group has occurred. Photolysis in solution leads to addition of the solvent to the unsaturated ketone. Some interest has centred on the partial synthesis of gibberellin Ajg (105), whose total synthesis was reported earlier. Details of the conversion of gibberellin A g into some 5-lactones related to gibberellin A15, and on the partial synthesis of gibberellin Ajg nor-ketone from 7-hydroxykaurenolide, reported... 

A useful method has been developed for converting the readily accessible 3-hydroxy-gibberellins into 2-hydroxy-gibberellins and it has been applied to the partial synthesis of two new gibberellins, A46 (74), isolated from Echinocystis macrocarpa (Cucurbitaceae), and A47 (75), isolated from the fungus Gibberella... 

Figure 2.7 shows my idea at the time when I finished the synthesis of ( )-epigibberic acid to convert it to gibberellin A4. A phenolic compound A can be prepared from ( )-epigibberic acid (18). Reduction of the... 

Interest in the structure-activity relationships of the gibberellins has led to the partial synthesis of the four stereoisomers about positions 5 and 6 of the hexa-hydrofluorene (57). The unsaturated acid anhydride (56) was prepared by the benzilic acid ring-contraction of the 6,7-diketones obtained from oxidation of desisopropyl dehydroabietic acid, and converted into the saturated acids by reduction and base-catalysed epimerisation. 

A partial synthesis of gibberellin Ajj nor-ketone from 7-hydroxykaurenolide has been described. The key stage in this synthesis is the activation of the C-20 methyl group by photolysis of a C-19 amide (173). 

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