Michael additions and reactions with haloalkanes have demonstrated the synthetic usefulness of the C-2 and C-4 anions in ceph-3-em sulphides and sulphoxides for the formation of a range of novel compounds (A-H). Other compounds prepared from similiar reactions include (I-O). A reverse Michael addition was attempted on the C-4 mono-adducts (M) and (N) and di-adducts (L) and (O). Determination of the configuration of the di-adducts (F) and (I) was accomplished by de-esterification followed by decarboxylation and resulted in the novel ceph-3-em (P). Conversion of (J) and (K) into novel ceph-3-ems (Q) and (R) bearing C-2 exocyclic bond systems via a Pummerer rearrangement is described. Attempts at a Pummerer rearrangement of (D) and (E) failed. Numerous attempts at a Cope rearrangement on ceph-2-em sulphoxide (G) and sulphide (H) failed. De-esterification reactions of the new ceph-3-ems to their corresponding acids were unsuccessful.
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