https://chemistry.mdma.ch/hiveboard/rhodium/pdf/indole.synth.review.1994-99.pdf

Recent developments in indole ring synthesis—methodology and applications

Transition Metal Complexes Containing Allenylidene, Cumulenylidene, and Related Ligands.

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/pdf/metal-assisted-cycloaddition-reactions-in-organotransition-2cf6yzr4gb.pdf

Metal-Assisted Cycloaddition Reactions in Organotransition Metal Chemistry

The formal combination of a carbene and an organometallic fragment yields carbene complexes. They are commonly classified as Fischerand Schrock-type complexes. While Schrock-type compounds (first described in the early 1970s) play an important role in olefin metathesis (acknowledged by the Nobel Prize 20051), Fischer carbene complexes, which were first reported in 19642a and 1965,2b have been developed into powerful reagents for organic synthesis.3 This review concentrates on group 6 metal carbene complexes with a special focus on chromium complexes since, because of their balance of reactivity and stability combined with easy accessibility (see below), they are the most prominent members of the Fischer carbenes and have found the broadest application. While most of the recent chemistry of Fischer carbene complexes has been periodically summarized during the last 5-10 years,4 this review, apart from the basic characteristics of Fischer carbene complexes in the introductory part, will focus on the developments since the mid1990s. The literature is covered up to April 2009.

Fischer Carbene Complexes in Organic Synthesis: Metal-Assisted and Metal-Templated Reactions

The metal carbene complexes, discovered by E. O. Fischer at the start of the 1960s and carrying his name, have since proved themselves to be irreplaceable building blocks for organic synthesis. In particular, since the discovery of the Dotz reaction, a formal cycloaddition of Fischer alpha,beta-unsaturated carbene complexes to alkynes with CO insertion, this area of chemistry has become increasingly interesting to organic chemists. In spite of the considerable diversity of reactions performed with these complexes, proper selection of substrates and careful adjustment of the reaction conditions have allowed, in most cases the perfectly selective preparation of individual compounds of this enormous range of products. The spectrum of new successes begins with the conventional Diels-Alder reaction of alkynylcarbene complexes and the formal regioselective [3+2] cycloaddition of alkenylcarbene complexes to alkynes. It extends much further, however, from cascade reactions with the formation of oligofunctional and oligocyclic products of impressive molecular complexity to complex, formal [3+6] cocyclizations in which six bonds are formed in a single operational step. Beyond doubt, the methodological arsenal of preparative organic chemistry cannot be imagined any more without the valuable transformations of the Fischer carbene complexes; it only remains to be seen whether one or other of the numerous new types of cocyclization products of these complexes can establish itself as a lead structure in the search for biologically active compounds.

Fischer Carbene Complexes as Chemical Multitalents: The Incredible Range of Products from Carbenepentacarbonylmetal alpha,beta-Unsaturated Complexes.

The first Michael addition reactions of the anions of aminocarbene complexes to α,β-unsaturated carbonyl compounds are reported. Unlike their corresponding amide enolates, these anions give exclusive 1,4-addition to a number of enones. For chiral complex 27, it was shown that the formation of the 1,4-addition product is not reversible and that the initial 1,4-addition is thus kinetically controlled. The anions of aminocarbene complexes are much more effective in this regard than the anions of alkoxycarbene complexes. It was demonstrated that aminocarbene complexes can serve as synthons for amides in Michael additions since the metal can be liberated from the Michael adducts to give amide products by oxidation with either DMSO or dimethyldioxirane

Asymmetric Michael reactions of aminocarbene complex anions

Phenol formation from the reactions of amino-stabilized alkenyl fischer carbene complexes

Preparation, characterization, and reactions of the first parent acetylene Fischer carbene complexes

Moore-Type Cyclization Leading to Arene Chromium Tricarbonyl 1,4-Diradical Intermediates and the Isolation of Indolines

https://www2.chemistry.msu.edu/faculty/wulff/myweb26/Publications/image_paper/119.pdf

Annette Rahm

Papers

Asymmetric Michael reactions of aminocarbene complex anions

Phenol formation from the reactions of amino-stabilized alkenyl fischer carbene complexes

Preparation, characterization, and reactions of the first parent acetylene Fischer carbene complexes

Moore-Type Cyclization Leading to Arene Chromium Tricarbonyl 1,4-Diradical Intermediates and the Isolation of Indolines

Asymmetric Diels-Alder Reactions with Chiral Acetylenic Carbene Complexes as Dienophiles