3-Thioxo-3 H -indolizinium-1-olates and Related Pseudo-Cross-Conjugated Heterocyclic Mesomeric Betaines: Synthesis and Spectral Features.

The first example of the synthesis of 3-thioxo-3 H -indolizinium-1-olates, which further expands a limited class of pseudocross-conjugated heterocyclic mesomeric betaines isoconjugate to odd nonalternant hydrocarbon anion, is reported. These unique, moderately colored heterocyclic products result from a developed three-component reaction of cyclopropenones, pyridines, and sulfur. The protocol is distinguished by simple and mild reaction conditions that avoid expensive reagents or exotic catalysts, exhibiting high functional group tolerance. The broad scope of the reaction is particularly remarkable in light of the dramatic influence of pyridines' substituents on the reactivity of corresponding indolizin-1-ols, the key intermediates that proved to be highly thiophilic. In addition, an oxidative coupling of indolizin-1-ol in situ with p -tropoquinone oxime acetate is discovered. The reaction involves the C3 and C5 positions of the indolizin-1-ol and results in unusual indolizine-aminotropolone combinations. For the 3 H -indolizinium-1-olate type of PCC HMBs, some general considerations concerning light absorption and NMR regularities were formulated.