Patent ID: 8067632

Claim:
A process to produce a 12-deoxy tigliane-type compound or a structural analog thereof of the formula: Formula I wherein R 1 is selected from the group consisting of hydrogen, alkyl (C1 to C15), cyclic alkyl (C3 to C15), aromatic ring, hydroxyl, carbonate, carbamate, ester, ether, thiol, amine, amide, guanidine and urea; R 2 is selected from the group consisting of hydrogen, alkyl (C1 to C15), cyclic alkyl (C3 to C15), aromatic ring, hydroxyl, carbonate, carbamate, ester, ether, thiol, amine, amide, guanidine and urea; R 3 is selected from the group consisting of hydrogen, alkyl (C1 to C15), cyclic alkyl (C3 to C15), aromatic ring, hydroxyl, carbonate, carbamate, ester, ether, thiol, amine, amide, guanidine and urea; R 4 is selected from the group consisting of hydrogen, alkyl (C1 to C15), cyclic alkyl (C3 to C15), aromatic ring, hydroxyl, carbonate, carbamate, ester, ether, thiol, amine, amide, guanidine and urea; R 5 is selected from the group consisting of hydrogen, alkyl (C1 to C15), cyclic alkyl (C3 to C15), aromatic ring, hydroxyl, carbonate, carbamate, ester, ether, thiol, amine, amide, guanidine and urea; and R 6 is selected from the group consisting of hydrogen, alkyl (C1 to C15), cyclic alkyl (C3 to C15), aromatic ring, hydroxyl, carbonate, carbamate, ester, ether, thiol, amine, amide, guanidine and urea; with the proviso that R 1 and R 6 cannot both be hydrogen and wherein R 1 and R 6 may be connected as in the case of 12-deoxy tigliane-type compounds, or may be disconnected as in the case of structural analogs, said process comprising: a) contacting an enolate salt, enol ester, enol ether or a ketone at the position corresponding to C-13 of a compound, said compound possessing structural features of a C ring of a tigliane and possessing a C-14 linked to at least a propenyl group, with hydrazine or an agent equivalent to hydrazine at a temperature between −20 and +150° C. for about 0.1 to about 72 hours; b) contacting the product of step a with an organic solvent at approximately +20 to +250° C. to form a pyrazoline product; c) contacting the product of step b with an oxidizing agent which is an electron withdrawing compound or nucleophilic agent in an organic solvent at between about −10 to +120° C. for approximately 0.1 to 72 hours to form a product oxidized at said C13 position; d) forming from the product of step c) a compound of Formula I by 1) contacting the product of step c with light of a wavelength that is absorbed by the product in a solvent at between about −20 and +60° C. for between about 1 to 240 min; or 2) contacting the product of step c with an excited state of a sensitizer formed by absorption of light by the sensitizer; or 3) contacting the product of step c with a metal or metal salt in an organic solvent at between about −80 and +110° C. for between about 1 and 48 hours; and e) isolating the compound of Formula I from the product of step d).