Acetylides organometallic

High MW, rigid-rod, conjugated transition metal acetylide polymers (42, Scheme 10) were synthesized by reaction of the dichloro iron or ruthenium chelated diphosphine complexes (40) with a te-trimethylstannylacetylide monomer (41). Reaction of the rhodium complex 43 with an equimolar amount of compound 44 gave a rigid-rod acetylide organometallic polymer 45 (Scheme 11). This ihodium-containing polymer was soluble in THE... 

The properties of organometallic compounds are much different from those of the other classes we have studied to this point Most important many organometallic com pounds are powerful sources of nucleophilic carbon something that makes them espe cially valuable to the synthetic organic chemist For example the preparation of alkynes by the reaction of sodium acetylide with alkyl halides (Section 9 6) depends on the presence of a negatively charged nucleophilic carbon m acetylide ion... 

Organometallics, such as dialkyl zinc or cadmium-alkyl or aryl lithium Alkali acetylides Diels-Alder Arndt-Eistert... 

You have already had considerable experience with caibanionic compounds and their- applications in synthetic organic chemistry. The first was acetylide ion in Chapter 9, followed in Chapter 14 by organometallic compounds—Grignaid reagents, for exanple—that act as sources of negatively polarized car bon. In Chapter 18 you learned that enolate ions—reactive intermediates generated from aldehydes and ketones—are nucleophilic, and that this property can be used to advantage as a method for carbon-carbon bond formation. 

The most ionic of the organometallic derivatives of Group 1 elements are the acetylides and dicarbides formed by the deprotonation of alkynes in liquid ammonia solutions ... 

Especially in the early steps of the synthesis of a complex molecule, there are plenty of examples in which epoxides are allowed to react with organometallic reagents. In particular, treatment of enantiomerically pure terminal epoxides with alkyl-, alkenyl-, or aryl-Grignard reagents in the presence of catalytic amounts of a copper salt, corresponding cuprates, or metal acetylides via alanate chemistry, provides a general route to optically active substituted alcohols useful as valuable building blocks in complex syntheses. 

Keywords. Metallodendrimer, Organometallic complex. Metal acetylide... 

The alkynyl-metal (metal-acetyhde) complex is one of the best building blocks for organometallic dendrimers, since it has some advantages compared to other organometallic complexes [18]. Most of the metal-acetylide complexes are thermally robust and stable, even when exposed to air and moisture. Metal-acetylide complexes are fairly accessible in high yields by well-established synthetic methodology [19]. These features are essential to the construction of dendrimers. 

Metal-acetylide complexes have been used as a unit of organometallic polymers that have metallic species in the main chain [20]. Representative examples are metal-poly(yne) polymers (19) of group 10 metals depicted in Scheme 5. These polymers are easily prepared from M(PR3)2Cl2 (M=Pt, Pd) and dialkynyl compounds catalyzed by Cu(I) salts in amine. Recently, this synthetic method was successfully applied to the construction of metal-acetylide dendrimers. 

It occurs with the alkyls, aryls or acetylides of metals more electropositive than magnesium, but including Grignard reagents, and is often carried out by adding a solution of the organometallic compound in an inert solvent to a large excess of powdered, solid C02 it is a particularly useful method for the preparation of acetylenic acids. The Kolbe-Schmidt reaction (p. 291) is another example of carbanion carbonation. 

Organometallic complexes of copper, nickel, and palladium have been used in indole syntheses from arenes. Most of the reactions proceed under relatively mild conditions and in some cases give rise to formation of the less common 2-substituted compounds.68 Good yields of such 2-substituted derivatives are formed in reactions of o-iodoarylamines with cuprous acetylides in dimethylformamide (Scheme 41 ).69 The efficiency of this type of... 

Ethyl 2,3-epoxypropanoate is a very interesting chiron. It may be opened by various organometallic compounds such as dialkyl, diaryl, and divinyl lithium cuprates, dialkylmagnesium cuprates, trialkylalanes and aluminum acetylides.5 6 The epoxide ring is attacked regiospecifically at the p-position and produces a-hydroxy esters exclusively without racemization. The same result is observed with... 

ALKYLALUMINIUM DERIVATIVES, ALKYLBORANES, ALKYLHALOBORANES ALKYLHALOPHOSPHINES, ALKYLHALOSILANES, ALKYLMETALS ALKYLNON-METAL HYDRIDES, ALKYLPHOSPHINES, ALKYLSILANES ARYLMETALS, BORANES, CARBONYLMETALS, COMPLEX ACETYLIDES COMPLEX HYDRIDES, HALOACETYLENE DERIVATIVES HEXAMETHYLNITRATODIALUMINATE SALTS, METAL HYDRIDES NON-METAL HYDRIDES, ORGANOMETALLICS, PYROPHORIC ALLOYS PYROPHORIC CATALYSTS, PYROPHORIC IRON-SULFUR COMPOUNDS PYROPHORIC METALS... 

The total of the reactions 2-5 results in reaction 1. The oxidative addition and formation of copper acetylide are well known. The intermetal transfer of the alkynyl group from copper acetylide (e.g., from Cu(I) to Pd(II) [8]) has been revealed by organometallic chemistry [8-11]. 

Acetylide (RC=CNa) and alkynide (RC=CMgX and RC=CLi) are good nucleophiles. They react with carhonyl group to from alkoxide, which under acidic work-up gives alcohol. The addition of acelylides and alkynides produces similar alcohols to organometallic reagents. 

Isomerization of a-hydroxy alkynes and alkynones 2-15 Acylation of olefins 2-27 From lithium acetylides 2-32 From vinylic organometallic compounds... 

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