Iron Catalysis in Organic Synthesis

1.1. General Reactivity of Alkyne-Gold(I) Complexes
For centuries, gold had been considered a precious, purely decorative inert metal. It was not until 1986 that Ito and Hayashi described the first application of gold(I) in homogeneous catalysis.1 More than one decade later, the first examples of gold(I) activation of alkynes were reported by Teles2 and Tanaka,3 revealing the potential of gold(I) in organic synthesis. Now, gold(I) complexes are the most effective catalysts for the electrophilic activation of alkynes under homogeneous conditions, and a broad range of versatile synthetic tools have been developed for the construction of carbon–carbon or carbon–heteroatom bonds.

Gold(I) complexes selectively activate π-bonds of alkynes in complex molecular settings,4−10 which has been attributed to relativistic effects.11−13 In general, no other electrophilic late transition metal shows the breadth of synthetic applications of homogeneous gold(I) catalysts, although in occasions less Lewis acidic Pt(II) or Ag(I) complexes can be used as an alternative,9,10,14,15 particularly in the context of the activation of alkenes.16,17 Highly electrophilic Ga(III)18−22 and In(III)23,24 salts can also be used as catalysts, although often higher catalyst loadings are required.

In general, the nucleophilic Markovnikov attack to η2-[AuL]+-activated alkynes 1 forms trans-alkenyl-gold complexes 2 as intermediates (Scheme 1).4,5a,9,10,12,25−29 This activation mode also occurs in gold-catalyzed cycloisomerizations of 1,n-enynes and in hydroarylation reactions, in which the alkene or the arene act as the nucleophile.



Scheme 1

Anti-Nucleophilic Attack to η2-[AuL]+-Activated Alkynes

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Gold(I)-Catalyzed Activation of Alkynes for the Construction of Molecular Complexity

A.L.-P. thanks CSIC for a contract under the JAE-doctor
program. Financial support by PLE2009 project from MCIINN
and Consolider-Ingenio 2010 (proyecto MULTICAT) are also
acknowledged.

Gold-catalyzed carbon-heteroatom bond-forming reactions.

Late transition metal-catalyzed hydroamination and hydroamidation.

Stereocontrolled Domino Reactions

Efficient synthesis of N-2-aryl-1,2,3-triazole fluorophores via post-triazole arylation.

Iron-Catalyzed C−O Bond Activation for the Synthesis of Propargyl-1,2,3-triazoles and 1,1-Bis-triazoles

1,2,3-Triazole as a special "X-factor" in promoting hashmi phenol synthesis.

Conformational control in the regioselective synthesis of N-2-substituted-1,2,3-triazoles.

Double the fun: The title reaction was developed by using a Lewis base/iminium activation strategy (see scheme). The reaction proceeded with excellent yields and ee values, and the products were additionally transformed into a single enantiomer of a substituted pyrrolidine with excellent retention of configuration.

Yunfeng Chen

Papers

Efficient synthesis of N-2-aryl-1,2,3-triazole fluorophores via post-triazole arylation.

Iron-Catalyzed C−O Bond Activation for the Synthesis of Propargyl-1,2,3-triazoles and 1,1-Bis-triazoles

1,2,3-Triazole as a special "X-factor" in promoting hashmi phenol synthesis.

Conformational control in the regioselective synthesis of N-2-substituted-1,2,3-triazoles.

Enantioselective Intermolecular Crossed-Conjugate Additions between Nitroalkenes and α,β-Enals through a Dual Activation Strategy†