Dienamines with acetylenedicarboxylates

The reaction of methyl propiolate (82) with acyclic enamines produces acyclic dienamines (100), as was the case with dimethyl acetylenedicarboxylate, and the treatment of the pyrrolidine enamines of cycloheptanone, cyclooctanone, cycloundecanone, and cyclododecanone with methyl propiolate results in ring enlargement products (100,101). When the enamines of cyclohexanone are allowed to react with methyl propiolate, rather anomalous products are formed (100). The pyrrolidine enamine of cyclopentanone forms stable 1,2-cycloaddition adduct 83 with methyl propiolate (82). Adduct 83 rearranges to the simple alkylation product 84 upon standing at room temperature, and heating 83 to about 90° causes ring expansion to 85 (97,100). 

There are numerous studies on the synthesis of pyrrolizines from enam-ines. In these reactions, one of the step is the closure to a new hydrogenated pyrrole ring. In polar solvents, the reaction of enamines with dimethyl acetylenedicarboxylate follows two different pathways, the formation of cycloadducts (18) and Michael adducts (19) (81T3525). Subsequent studies of this reaction have demonstrated (by low-temperature NMR) that compounds of the type 20 are intermediates in this cyclization (83JA4775). On the basis of this information (83JA4775), the authors then studied this type of cyclization using dienamines (21). The reaction follows the scheme shown, with a [1,6] antarafacial hydrogen shift and the formation of a dipo-... 

The course of the reaction of pyrrolidinostilbene with dimethyl acetylenedicarboxylate is solvent-dependent in apolar solvents, such as ether or toluene, the dienamine 57 is formed by ring-opening of an intermediate cyclobutene, whereas in methanol the pyrrolizine 59 is the main product. The pyrrolizine is thought to arise from an initial betaine which rearranges to the ylide 58 by a proton shift. Cyclization then gives the pyrrolizine (equation 31)53. 

Dimethyl acetylenedicarboxylate reacts with s-cis dienamines to give the cyclobutene adduct or the cyclo-octatriene ring expansion product depending on the nature of the substituent at C-4 of the dienamines25 (Scheme 16). 

Most heterocycles that contain a 1,3-dienamine moiety react as a diene and give Diels-Alder adducts. However, 3-dimethylamino-7,8-dihydro-2if-oxocin (30) has been claimed to give a (2 + 2)-cycloadduct (31) with dimethyl acetylenedicarboxylate (Section IV,B,2).5S... 

---