Recent advances in decarbonylative annulation reactions.

In recent years, decarbonylative annulation reactions have emerged as one of the most efficient routes to construct a variety of important carbocyclic and heterocyclic scaffolds. The main advantages of this type of reaction are, first, the carbonyl compounds are used as the starting materials which are abundant in nature and second, the major by-product of this reaction is carbon monoxide. In the last two decades, various intramolecular and intermolecular decarbonylative annulation reactions have been performed using carbonyl compounds and alkenes/alkynes/arenes/isocyanates etc. as the annulation partners. These reactions are typically performed either in the presence of or in the absence of a metal catalyst. However, these reactions are still in their infancy as a very little progress has been achieved in these reactions. Through this review article, it is attempted to highlight the recent developments on various decarbonylative annulation reactions which ultimately lead to the formation of important structural moieties.

Ru(ii)-Catalyzed cascade decarbonylative annulation and dehydrogenative alkenylation reactions: synthesis of phthalides.

A novel Ru(ii)-catalyzed decarbonylative annulation and direct C-H functionalization reaction of phthalic anhydrides with acrylates is reported. This reaction provides an efficient route for the synthesis of 3,7-disubstituted phthalides.

Carbon-Carbon Bond Cleavage Reaction: Synthesis of Multisubstituted Pyrazolo[1,5-a]pyrimidines.

A new carbon-carbon bond cleavage reaction was developed for the efficient synthesis of multisubstituted pyrazolo[1,5-a]pyrimidines. This base induced reaction of 1,3,5-trisubstituted pentane-1,5-diones and substituted pyrazoles afforded good yields of the pyrazolo[1,5-a]pyrimidines.

Ru(II)-Catalyzed and Ligand-Controlled C-H Activation and Annulation via 1,2-Phenyl Shift: Synthesis of Quaternary Carbon-Centered Pyrimidoindolones.

A novel Ru(II)-catalyzed C-H activation and annulation reaction of N-arylpyrazol-5-ones and diaryl/arylalkyl-substituted alkynes is developed. Unlike the reported metal-catalyzed C-H activation and annulation reactions, in the present bidentate amine-ligand controlled C-H activation and annulation reaction, the annulation occurs via a 1,2-aryl shift to afford quaternary carbon-centered pyrimidoindolones.

An efficient route for annulation of pyrimidines to steroids and non-steroids via a base catalyzed one-pot three component reaction.

A facile strategy for the synthesis of steroidal A- and D-ring fused pyrimidines has been accomplished in high yields via a one-pot reaction of steroidal ketones, aromatic aldehydes and amidine derivatives in presence of potassium tert-butoxide in refluxing ethanol. The generality of the reaction was also extended to non-steroidal ketones.

Synthesis of steroidal and nonsteroidal vicinal heterocyclic alcohols, N-(1-cycloalkenyl)heterocycles and their antibacterial studies.

A solvent free steroidal and nonsteroidal epoxide ring opening reaction by nitrogen containing heterocycles under microwave irradiation is described. Some of the epoxide ring opening compounds were converted to their corresponding N-(1-cycloalkenyl)heterocycles via an acid catalyzed dehydration reaction. The antimicrobial activities of the epoxide ring opening compounds and N-(1-cycloalkenyl)heterocyclic compounds were tested by agar diffusion assay. Compounds 6, 9-12, 24 and 27 showed moderate inhibition against the growth of pathogenic bacteria Escherichia coli, Pseudomonas syringae, Bacillus subtilis, Proteus vulgaris and Staphylococcus aureus.

Microwave-promoted and Lewis acid catalysed synthesis of steroidal A- and D-ring fused 4,6-diarylpyridines.

The preparation of novel steroidal heterocycles containing 4,6-diaryl substituted pyridine moiety fused to the 2,3- and 16,17-positions of the steroid nucleus is described. The Michael reaction of steroidal ketones (1a, 1b and 1c) with in situ generated chalcones provided the intermediates 3,5-diaryl-1,5-dicarbonyl steroidal derivatives (4a-s). Subsequently, the intermediates 4a-s were converted to the pyridine derivatives (5a-s) by solid phase reaction with urea in presence of BF3.OEt2 as the catalyst under microwave irradiation. All the synthesized heterosteroids are new compounds and are currently being evaluated for their biological activities.