Organic halides reactions with

The stoichiometric reaction of allenes with Pd(II) is treated in Chapter 3, Section 9, and catalytic reactions with organic halides are in this chapter, Section 1.1,1.3 Other catalytic reactions of allenes are surveyed in this section. 

Acidic chloroaluminate ionic liquids have already been described as both solvents and catalysts for reactions conventionally catalyzed by AICI3, such as catalytic Friedel-Crafts alkylation [35] or stoichiometric Friedel-Crafts acylation [36], in Section 5.1. In a very similar manner, Lewis-acidic transition metal complexes can form complex anions by reaction with organic halide salts. Seddon and co-workers, for example, patented a Friedel-Crafts acylation process based on an acidic chloro-ferrate ionic liquid catalyst [37]. 

Metallic zinc is typically covered with a zinc oxide layer that must be removed before the metal can engage in an oxidative addition reaction with organic halides. This activation can be done in one of several ways. 

Upon reaction with organic halides, trialkylplumbylsodium163 or triphenylplumbyllit-hium164 are converted into useful organoplumbanes with additional functionalities, such as... 

The added advantage of the C (1 )-stannylated glycals is their abUity to participate in palladium-catalyzed coupling reactions with organic halides, a process independently reported by Beau [75] and Friesen [81]. Vinyl stannane 237 can be benzylated, allylated or acylated provided that appropriate catalysts are used [75,77] and representative examples are given in Scheme 59. The C-arylation of... 

MgCl+ ions undergo anion abstraction reactions with organic halides (equation and nitric acid (equation 31). 

Generally, tin vapor appears only slightly more reactive than finely divided tin in its reactions with organic halides (55). 

TBAF has been modified structurally around the anion to reduce its hygroscopic property. Several such reagents have been reported and their reaction with organic halides and sulfonate esters have been described. Tetrabutylammonium difluoride is ascribed to be a stable reagent and easily displaces halides and sulfonate esters.215 1-Dodecyl tosylate (18) is thus converted into 1-fluorododecane (19) in 96% yield. 

Some neutral metal carbonyls, particularly coordinatively unsaturated ones, are sufficiendy nucleophilic to undergo reaction with organic halides. Sigma-alkyl species which undergo subsequent CO insertion are formed by such reactions27. Hence, carbonylations... 

Reaction with organic halides leads to coupling products (63). From benzyl chloride and lithium />-toluoyltricarbonyl nickelate, a 73% yield of a-benzyl p-toluoin is obtained. The reaction presumably involves the initial formation of p-tolyl benzyl ketone, which reacts with a further... 

Bis(r 6-aryl) derivatives of molybdenum have been prepared by the co-condensation of the arene and molybdenum atoms at 77 K.305 Friedel-Crafts reactions catalysed by [(r 6-arene)Mo(CO)3] complexes have been developed further, and such reactions with organic halides shown to proceed via an ionic mechanism.306... 

Solutions of diaryldialkaligermanes were prepared by the reaction of alkali metals with the corresponding arylgermanes in HMPA/THF (equation 2)12. Aryldialkaligermanes have never been isolated, but their formation was chemically confirmed by the Ar2GeD2 formed by deuteriolysis. Their reaction with organic halides was not taken as sufficient evidence of their formation. In 13C NMR they show a deshielded ipso aromatic carbon compared... 

However, as also observed in germanium chemistry, a mixture of dihydride with an excess of lithiated reagent behaves as a stannyldianion in reactions with organic halides, polyformaldehyde or epoxides (Scheme 7)29, and it thus appears as an interesting synthetic reagent. 

---