Acyl chlorides reaction with aziridine

Aziridines can add to carbon—carbon multiple bonds. Elevated temperature and alkali metal catalysis are required in the case of nonpolarized double bonds (193—195). On the other hand, the addition of aziridines onto the conjugated polarized double or triple bonds of a,p-unsaturated nitriles (196—199), ketones (197,200), esters (201—205), amides (197), sulfones (206—209), or quinones (210—212) in a Michael addition-type reaction frequendy proceeds even at room temperature without a catalyst. The adducts obtained from the reaction of aziridines with a,p-unsaturated ketones, eg, 4-aziridinyl-2-butanone [503-12-8] from 3-buten-2-one, can be converted to 1,3-substituted pyrrolidines by subsequent ring opening with acyl chlorides and alkaline cyclization (213). 

Acyl chlorides react with epoxides in the presence of a Eu(dpm)3 catalyst or a YCp2Cl catalyst (where Cp is cyclopentadienyl) to give chloro esters. A related reaction with epi-sulfides leads to 2-chlorothio-esters. Aziridines have been opened with MgBr2 to give 2-haloamides in a related reaction. 

Alternatively, the remaining sulfate ester of 70 may serve as a leaving group for a second nucleophilic displacement reaction. When this displacement is by an intramolecular nucleophile, a new ring is formed, as was first shown in the synthesis of a cyclopropane with malonate as the nucleophile [68] and of aziridines with amines as the nucleophiles [76]. The concept is further illustrated in the double displacement on (/J,/ )-stilbenediol cyclic sulfate (72) by benzamidine (73) to produce the chiral imidazoline 74 [79]. Conversion of the imidazoline (74) to (.V,.S )-stilbenediaminc 75 demonstrates an alternative route to optically active 1,2-diamines. Acylation of 75 with chloroacetyl chloride forms a bisamide, which, after reduction with diborane, is cyclized to the enantiomerically pure trans-2,3-diphenyl- 1,4-diazabicy-clo[2.2.2]octane (76) [81],... 

Compound 48 is 0-mesylated at C(3) with methanesulfonyl chloride in pyridine to obtain 49, and this is then treated with sodium hydroxide in hot 2-methoxyethanoI to instigate ring closure to the epimine 44. Because A-acyl aziridines are base-labile, the A-deprotected aziridine 44 is the final product that actually emerges from this reaction, which was highly desirable for the purposes we had in mind. 

Alkylation of flra-chloroaniline (13-1) with 2,2,2-triiluoroethyl trichloromethyl-sulfonate affords the corresponding trifluroethylated derivative (13-2). Reaction of the anion from that with aziridine proper leads to the formation of the diamine (13-3). Acylation of that compound with ortfio-fluorobenzoyl chloride (13-4) proceeds to... 

Indolyl A-Grignards, "" or even better their zinc analogues, undergo reaction predominantly at C-3 with a variety of carbon electrophiles such as aldehydes, ketones and acid halides, or reactive halo-hetero-cycles. Including aluminium chloride in the zinc reactions produces high yields of 3-acyl-indoles. The copper-catalysed reactions of indolyl-A-Grignards with A-t-butoxycarbonyl-aziridines also proceed well at C-3. ... 

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