Organomanganese reagents

See page 101, Section 2.3, for the iron catalyzed cross-coupling of RMgX and ArX. 

See page 1528, Section 22 page 1724, Section 2 and page 1801, Section 6, respectively. 

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Organomanganese reagents can be used for the formation of ketones from acid chlorides with excellent functional group tolerance, the corresponding ketones isolated in good yield. Gallo et al. have reported some hetero-... 

Copper-Catalyzed Alkylation of Organomanganese Reagents Preparation of 2,2-Dimethyldecane from tert-Butyl Manganese Chloride. 

Organomanganese reagents have also been used to prepare numerous simple or functionalized ketones in high yields.10 They can be also used to carry out in high yields, at room temperature, various chemoselective 1,2-addition reactions, for example to keto aldehydes.11... 

Good yields of 1,4-addition products have also been obtained with alkylidene malonate esters which generally react with organomanganese reagents in the absence of copper salts9 (see Table IV). 

In conclusion, copper-manganese-catalyzed organomagnesium reagents and copper-catalyzed organomanganese reagents are a simple, efficient, and economic alternative to copper-catalyzed organomagnesium reagents and especially to... 

Scheme 2.S7. Copper-catalyzed Michael addition reactions between organomanganese reagents and pulegone.

Alkylation of organomanganese reagents with alkyl bromides can also be improved by addition of CuCI (3 mol%). The reactions proceed at room temperature and are complete within a few hours [123, 130], The opening of epoxides is also improved under these conditions. The reaction also features good chemoselectivity, tolerating the presence of sensitive functions such as ketones (Scheme 2.59) [130]. 

Benzylic organomanganese reagents prepared by direct insertion of activated manganese metal display the same behavior (Scheme 2.60) [131]. Excellent results are also obtained for 1,4-additions of organomanganese reagents to unsaturated esters in the presence of CuCI (3 mol%) [127]. 

Coupling reactions with organometallic reagents 4.2.1 Organomanganese reagents... 

Organomanganese reagents display a similar reactivity profile (Table 5.1, entries 16 and 17) [12]. Although the reaction rates are lower, yields and selectivities are generally high. 

G. Cahiez, J. Rivas-Enterrios, and P. Clery, Tetrahedron Letters, 29, 3659 (1988). Organomanganese reagents. 

A useM review on organomanganese reagents in organic synthesis has appeared. As described therein, one of the most stable alkyl Mn(II) reagents is trialkyl manganate, MnRs, which can be conveniently prepared as the Li+ or MgBr+ salt and used at 0 °C. These have been utilized for a variety of reactions, such as the stereoselective alkylation of gew-dibromocyclopropanes (Scheme 2), the silylation of acetylenes, and the radical cyclization of allylic ethers. Some of these transformations can be made catalytic. ... 

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