New Advances in Selected Transition Metal-Catalyzed Annulations

Abstract

This account describes the recent advances on the Pd-catalyzed [4+2]-benzannulation reaction, development of chemo- and regiospecific formal [2+2+2]-cyclotrimerization of alkynes, as well as discovery and evolution of the transition metal-catalyzed cycloisomerization of alkynyl ketones and imines into five-membered heteroaromatics.

• 1 Advances in Pd-Catalyzed Benzannulation Reactions

• 1.1 Introduction

• 1.2 Formal [2+2+2]-Trimerization of Alkynes

• 1.3 Acceleration of Benzannulation Reaction by Lewis Acids

• 1.4 Regioselectivity of the Benzannulation with Unsymmetrical Diynes

• 1.5 Palladium-Catalyzed Head-to-Head Coupling of Alkynes

• 1.6 Palladium-Catalyzed Cross-Coupling of Alkynes with Allenes

• 2 Novel Transition Metal-Catalyzed Cycloisomerization Reactions

• 2.1 Introduction

• 2.2 Cu-Catalyzed Cycloisomerization of Alkynyl Imines into Pyrroles

• 2.3 Cycloisomerization of Alkynyl Ketones into Furans

• 2.4 Investigation of the Mechanism of the Cu-Catalyzed Cycloisomerization Reaction

• 2.5 Formation of Unexpected Bicyclic Product

• 2.6 Multi-Substituted Heterocycles

• 2.6.1 Towards 3-Substituted Heterocycles

• 2.6.2 4-Substituted Heterocycles via 1,2-Migrations

• 2.6.3 Tetrasubstituted Furans

• 2.7 Fused Pyrroloheterocycles

• 2.8 Application of the Cycloisomerization Reaction to Synthesis of Alkaloid Structures

• 3 Conclusion

Key words

transition metal catalysis - benzannulation - cyclo­isomerization - cascade reactions - fused heteroaromatics

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3

See for discussion of alternative mechanisms ref. [2c]

8

Gevorgyan. V. Kel’in. A. V. Unpublished results.

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Significant deuterium scrambling between deuterated terminal alkynes and eventual proton sources in the presence of transition metals is well documented.

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