Halides, aryl, arylation alkoxides

Palladium complexes also catalyze the carbonylation of halides. Aryl (see 13-13), vinylic, benzylic, and allylic halides (especially iodides) can be converted to carboxylic esters with CO, an alcohol or alkoxide, and a palladium complex. Similar reactivity was reported with vinyl triflates. Use of an amine instead of the alcohol or alkoxide leads to an amide. Reaction with an amine, AJBN, CO, and a tetraalkyltin catalyst also leads to an amide. Similar reaction with an alcohol, under Xe irradiation, leads to the ester. Benzylic and allylic halides were converted to carboxylic acids electrocatalytically, with CO and a cobalt imine complex. Vinylic halides were similarly converted with CO and nickel cyanide, under phase-transfer conditions. ... 

Many Cu(I) compounds have polymeric structures with weak Cu—Cu bonds that are bridged by atoms or groups. These include Cu(I) carboxylates, alkyls and aryls, alkoxides and (CuXL) complexes (X = halide, L = ligand). In Cu(I) compounds Cu has a filled 3d shell, 3d , that does not participate in metal-metal bonding, so the extent of metal-metal bonding in these compounds is questionable. Calculations show that the metal-metal bonding is at best weak . These compounds arise from the same syntheses as would be used to prepare the monomer, and so they are not considered further here. 

Both Ni and Pd reactions are proposed to proceed via the general catalytic pathway shown in Scheme 8.1. Following the oxidative addition of a carbon-halogen bond to a coordinatively unsaturated zero valent metal centre (invariably formed in situ), displacement of the halide ligand by alkoxide and subsequent P-hydride elimination affords a Ni(II)/Pd(ll) aryl-hydride complex, which reductively eliminates the dehalogenated product and regenerates M(0)(NHC). ... 

The first palladium-catalyzed formation of aryl alkyl ethers in an intermolecular fashion occurred between activated aryl halides and alkoxides (Equation (28)), and the first formation of vinyl ethers occurred between activated vinyl halides and tin alkoxides (Equation (29)). Reactions of activated chloro- and bromoarenes with NaO-Z-Bu to form /-butyl aryl ethers occurred in the presence of palladium and DPPF as catalyst,107 while reactions of activated aryl halides with alcohols that could undergo /3-hydrogen elimination occurred in the presence of palladium and BINAP as catalyst.110 Reactions of NaO-/-Bu with unactivated aryl halides gave only modest yields of ether when catalyzed by aromatic bisphosphines.110 Similar chemistry occurred in the presence of nickel catalysts. In fact, nickel catalysts produced higher yields of silyl aryl ethers than palladium catalysts.108 The formation of diaryl ethers from activated aryl halides in the presence of palladium catalysts bearing DPPF or a CF3-subsituted DPPF was also reported 109... 

Although less common, ketyl anions can also be generated by removal of an a-hydrogen from an alkoxide (Figure 1, reaction 3). An interesting example where a ketyl anion is formed as an intermediate in this manner is provided by the electrochemically-initiated reduction of an aryl halide by an alkoxide anion via the free radical chain process illustrated in Scheme l6. 

Interestingly, this strategy was applied to the more reactive propargyl alkoxides allowing for the simultaneously introduction of the three partners at the start of the reaction. In fact, in this case, no side reactions occurred [95]. This process is remarkably versatile, giving good yields of stereodefined 3-arylidene (and alkenyli-dene) tetrahydrofurans 105 with a variety of propargyl alcohols (primary, secondary, and tertiary) and unsaturated halides (aryl iodides, vinyl bromides, and tri-flates) (Scheme 8.45). 

Certain ethers can be prepared by the reaction of unusually active aryl halides with sodium alkoxides. For example ... 

The reaction of triarylsulfonium halides with sodium alkoxides at high temperatures afforded mixtures of alkyl aryl ethers (24), diarylsulfides, hydrocarbons and aldol resins or a ketone if the alkoxide is derived from a secondary alcohol.25,36,38-41... 

The reaction of metal halides with an alkoxide or aryl oxide (most commonly an alkali metal alkoxide), can result in metathetic exchange to give the required complex (equation 6). Such reactions can also result in the formation of heterometallic species (such as NaZr2(OR)4) this can be a problem when homometallic alkoxides are desired, but it is an important route to heterometallic alkoxides and aryloxides. The nature of the product can be influenced by the alkali metal, the alkoxide ligand, and the relative amounts of the... 

The reaction between an alkoxide ion and an aryl halide can be used to prepare alkyl aryl ethers only when the aryl halide is one that reacts rapidly by the addition-elim mation mechanism of nucleophilic aromatic substitution (Section 23 6)... 

The reaction between acyl halides and alcohols or phenols is the best general method for the preparation of carboxylic esters. It is believed to proceed by a 8 2 mechanism. As with 10-8, the mechanism can be S l or tetrahedral. Pyridine catalyzes the reaction by the nucleophilic catalysis route (see 10-9). The reaction is of wide scope, and many functional groups do not interfere. A base is frequently added to combine with the HX formed. When aqueous alkali is used, this is called the Schotten-Baumann procedure, but pyridine is also frequently used. Both R and R may be primary, secondary, or tertiary alkyl or aryl. Enolic esters can also be prepared by this method, though C-acylation competes in these cases. In difficult cases, especially with hindered acids or tertiary R, the alkoxide can be used instead of the alcohol. Activated alumina has also been used as a catalyst, for tertiary R. Thallium salts of phenols give very high yields of phenolic esters. Phase-transfer catalysis has been used for hindered phenols. Zinc has been used to couple... 

Reaction between aryl halides and alkoxides or aroxides... 

Ligand A anionic (e.g., halides, pseudohalides, alkyl, aryl, thiolate, alkoxide) ligand N neutral (e.g., amines, imines, phosphines, carbenes, nitriles, isonitriles, NO, CO) ligand C cationic (e.g., NO+)... 

In contrast to the borylation of alkane C-H bonds, the coupling of aryl halides with amines was based on a literature precedent from another group published about a decade before our initial studies. Kosugi, Kameyama and Migita published the coupling of aryl halides with tin amides." Mechanistic studies we conducted on this process led us to the perhaps obvious realization that the reaction" could be conducted with amines and a silylamide base instead of tin amides (equation 4)." Surveys of bases with similar p a values led Janis Louie to conduct reactions with alkoxide bases. Similar studies were conducted at nearly the same time by Steve Buchwald and coworkers."... 

Alkoxide or aryloxide anions are also reputed to be inactive in Sr I reactions. There is, however, one example of such a reaction at an sp carbon the nitro-derivative of 4-nitrocumyl reacts with phenoxide and 1-methyl-2-naphthoxide ions yielding the corresponding ethers (Kornblum et al., 1967). A similar reaction has been reported for halobenzenes in t-butyl alcohol upon stimulation by sodium amalgam (Rajan and Sridaran, 1977). This reaction could not, however, be reproduced (Rossi and Pierini, 1980) and other attempts to make phenoxide ions react at sp carbons have been equally unsuccessful (Ciminale et al, 1978 Rossi and Bunnett, 1973 Semmelhack and Bargar, 1980). It has been found, more recently, that phenoxide ions react with a series of aryl halides under electrochemical induction, but that the coupling occurs at the p- or o-phenolic carbon rather than at the phenolic oxygen (Alam et al, 1988 Amatore et al, 1988). This is... 

Tab. 10.8 summarizes the application of rhodium-catalyzed allylic etherification to a variety of racemic secondary allylic carbonates, using the copper(I) alkoxide derived from 2,4-dimethyl-3-pentanol vide intro). Although the allyhc etherification is tolerant of linear alkyl substituents (entries 1-4), branched derivatives proved more challenging in terms of selectivity and turnover, the y-position being the first point at which branching does not appear to interfere with the substitution (entry 5). The allylic etherification also proved feasible for hydroxymethyl, alkene, and aryl substituents, albeit with lower selectivity (entries 6-9). This transformation is remarkably tolerant, given that the classical alkylation of a hindered metal alkoxide with a secondary alkyl halide would undoubtedly lead to elimination. Hence, regioselective rhodium-catalyzed allylic etherification with a secondary copper(l) alkoxide provides an important method for the synthesis of allylic ethers. 

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