Dehydrogenative Heck Annelations of Internal Alkynes

Abstract

This review covers the palladium-catalyzed annelations of internal alkynes through reactions leading to the loss of only two hydrogens from the substrates. They occur via (i) dual C–H bond activation, (ii) both C–H and N–H bond activation, (iii) successive amino(or oxy)palladation and C–H bond activation, or (iv) C–H bond activation followed by a Heck-type process. The proposed mechanisms are described with, in some cases, personal commentary.

1 Introduction

2 Synthesis of Aryl Rings

2.1 Via Aryl–Alkyne Coupling

2.2 Via Allylaryl–Alkyne Coupling

2.3 Via Cyclopentadienyl–Alkyne Coupling

2.4 Via Benzoylacetate–Alkyne Coupling

2.5 Via Indole–Alkyne Coupling

2.6 Via Benzothiophene–Alkyne or Benzofuran–Alkyne Coupling

3 Synthesis of Pyrrole Rings

3.1 Via Imidazo[1,2-a]pyridine–Alkyne Coupling

3.2 Via Aniline–Alkyne Coupling

3.3 Via Enamine–Alkyne Coupling

3.4 Via Enamide–Alkyne Coupling

3.5 Via Indole–Alkyne Coupling and Rearrangement

4 Synthesis of Pyridinone Rings

4.1 Via Indole-carboxamide–Alkyne Coupling

4.2 Via Arylcarboxamide–Alkyne Coupling

5 Synthesis of Furan Rings

6 Synthesis of Azepine Rings

7 Synthesis of Spiroindenes

8 Synthesis of Cyclopentadiene Rings

8.1 Via Arylalkyne Self-Coupling

8.2 Via Alkenylindole–Alkyne Coupling

9 Conclusion

Key words

alkynes - annulation - Heck reaction - palladium - palladacycles

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