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Approaches to the synthesis of penicillin

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  • Several approaches to the synthesis of penicillin from 2-iminothioazolidine 50, from 2-thiothiazolidine 66 and by photocyclization of 77 and 78 were investigated. 2-Iminothiazolidine 50 was prepared from dibromoester 45 by the action of benzylamine followed by treatment of aziridine 46 with potassium or ammonium thiocyanate. Attempted introduction of a two-carbon unit into 50 by decomposition of ethyl diazoacetate afforded 51 and 52. Similarly, acetyl derivative 53 gave a carbon-hydrogen insertion product 54 upon pyrolysis. The reaction of 53 with ethyl lithiodiazoacetate produced an unexpected product 55. The synthesis of 2-thiothiazolidines by their reaction of aziridine 56 with carbon disulfide or potassium thiocyanate yielded only the undesired thiazolidines 57 and 60 respectively. However, the reaction of 66 with diethyl bromomalonate gave a 2-substituted thiazolidine 7G Reduction of 70 with sodium borohydride produced 71. Compounds 77 and 78 were synthesized by the coupling of 76 and 66 with phthalimidoacetyl chloride respectively. Attempted p-lactam formation by photolysis of 77 or 78 yielded only Norrish type II cleavage and no cyclization product. Biogenetically patterned approaches to the synthesis of 6-aminopenicillanic acid were also studied. Cysteine was protected at sulfur and nitrogen by the acetamidomethyl and tert-Boc groups respectively to give 86, which was condensed with aziridine 56 in the presence of DCC yielding 88. Photolysis of 88 followed by deprotection of sulfur gave the dimer 92. In another approach, a putative precursor of the thioaldehyde 89 was synthesized by a sequence in which cystine 93 was converted to N, N' -di-tert-Boc cystine 96 by treatment of tertbutoxycarbonylazide, the disulfide was cleaved by sodium metal in liquid ammonia, and the resulting thiol was immediately condensed with a-chloroacetophenone to give 97. Condensation of 97 with aziridine 56 in the presence of DCC produced 98 which upon photolysis afforded polymer.
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