Total synthesis of novel azetidinones, useful as...

C - Chemistry – Metallurgy – 07 – D

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C07D 499/00 (2006.01) C07D 205/09 (2006.01) C07D 499/88 (2006.01) C07F 9/568 (2006.01)

Patent

CA 1148143

FC-13 ABSTRACT OF THE DISCLOSURE A process is disclosed for the preparation of com- pounds of formula I: Image I wherein R is hydrogen, lower alkyl, trichloroethyl, benzyl, p-nitrobenzyl, acetoxymethyl, pivaloyloxymethyl, phthal- idyl, or a -CH(CH3)OCOOEt group; 1 is -CH2OH, - CHO, -CH2SH, - CH2NH2, -CH2OCOR2, -COOR2, -CH2NHCOR2, -CH2OR3, or -CH2SR4 where R2 is a lower alkyl, aryl or a heterocylic ring, R3 is a lower alkyl, benzyl, or trityl, and R4 is a five- or six-member heterocyclic ring containing one or more heteroatoms, which comprises reacting a 4-acetoxy azetidinone of formula II: Image II with a .beta.-thioketoester of formula: Image Abstract cont. to obtain a mixture of diasterioisomeric products of formula III: Image III which mixture is successively condensed with a glyoxylic ester of formula: Image to give a mixture of diastereoisomeric substituted carbinols of formula IV: Image IV reacting that mLxture with thionyl chloride to affoxd the corres- ponding chlorides of formula V: Image V which are transformed into their respective phosphorous ylids of formula VI: Abstract cont. Image VI ozonolysing the compounds of formula VI to obtain the corres- ponding phosphoranes of formula VII: Image VII and successively heating the so-obtained phosphoranes of formula VII to obtain the desired compounds of formula I. Especially preferred compounds are methyl(?)-2-acetoxyethyl-2-penam-3- carboxylate; acetoxymethyl (?)-3-ethoxycarbonylmethylene-7-oxe- 4-thia-1-azabicyclo-[3,2,0]-heptane-2-carboxylate; benzyl (?)- 3-ethoxycarbonylmethylene-7-oxo-4-thia-1-azabicyclo-[3,2,0]- heptane-2-carboxylate; and methyl (?)-3-ethoxycarbonylmethylene- 7-oxe-4-thia-1-azabicyclo-[3,2,0]-heptane-2-carboxylate. Compounds of formula (1) are potent irreversible inhibitors of different .beta.-lactamases as illustrated by a dramatic reduction of the MIC value of ampicillin against .beta.-lactamase producing bacteria. They also are endowed with antibacterial activity.

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