Allyl chloride 71-Ally 1 complexes

Ally] ethers and iodobenzene have also been added using a zirconium complex. Similarly, allyl ethers and allyl chlorides have been added. ... 

There is one report (193) of the formation of a hexa-l,3-dienemetal complex formed by a coupling reaction of the ally] ligands (method C) in the reaction of [Fe(PF3)5] with allyl chloride. 

The Pd-catalyzed a-allylation of esters was first achieved by the reactions of aUylic carbonates with ketene silyl acetals that can be generated by treating esters with McsSiCl in the presence of a base. The yields of the desired products based on ketene silyl acetals were generally good except in the allylation of lactones (Scheme Selection of solvents is critical since the use of nitriles, such as MeCN and PhCN, leads only to the formation of a,/3-unsaturated esters rather than the a-ally-lated products. Both Reformatsky reagents and lithium enolates of esters have also been successfully a-allylated in the presence of Pd catalysts (Scheme 10). A highly regio- and stereospecific allylation of y-butyrolactone with ( )-2-hexenyl acetate is noteworthy. Since the lithium enolate of esters would react with allylic chlorides even in the absence of a Pd catalyst, however, it is not clear to what extent the reaction is catalyzed by a Pd complex. 

Similarly, [M(CO)4diket] , where diket frequently is acac, reacts with ally lie chlorides (but not with bromides or iodides) forming [( -allyl)MCl(CO)2diket] for M = Mo and W. However, attempts with the corresponding Cr analogs fail. Also, anionic complexes [M(C0),RC02] (M = Mo, W) work welP. ... 

A number of investigations have explored the reactions of ally lie stannanes containing a y-alkoxy substituent. A direct preparation of these substances utilizes the kinetic deprotonation of an allyl ether followed by alkylation with tri-n-butylstannyl chloride. In a typical experiment, the deprotonation of 101 with 5-butyllithium leads to internal coordination of lithium cation and provides formation of the Z-allylstannane 102. The behavior of y-alkoxyallylstannanes is similar to the corresponding Z-alkylstannanes, and as a result, the reaction provides a stereoselective route for the synthesis of complex diol derivatives. In the allylation of chiral aldehyde 80 with stannane 102, /l-chelation dictates face selectivity. The expected. yyn, anti-product 104 is obtained with high diastereoselection via the antiperi-planar 103, which accommodates the sterically demanding silyl (TBS) ether (Scheme 5.2.23).23... 

The (7r-aIlyl)palIadium(II) complexes formed by oxidative addition have been extensively applied to catalytic organic synthesis. Representative examples are shovv n in eq (106)-(111) [139-142]. A variety of allyiic substrates have been employed as the source of the ally ligand, including allylic acetates, chlorides, epoxides, and carbonates. 

Whereas sodium indenide displays a stereoselectivity similar to phenylzinc chloride (see Table 26), sodium cyclopentadienide and 3-trimethylsilylindene act like soft carbanions. Both substrates 10 and 12 undergo allylic substitution with net retention of configuration to 1127 and 1328, respectively, via attack on the ally ligands of the intermediate 7t-allylpalladium complexes anti to the metal. Again, the ratio of the two possible diastereomers of structure 13 is unknown. 

Barbier reactions. Allylation of aromatic aldehydes in 0.1 N ammonium chloride solution using a combination of Mg and an allyl bromide or iodide (but not ally chloride) has been demonstrated." Unfortunately, aliphatic aldehydes give complex mixtures. However, conjugate addition to enones can be achieved with mediation by Cul. 

Carbonylation of ally lie alcohols requires severe conditions in generalJ The carbony-lation of allylic alcohols proceeds efficiently in the presence of LiCl and Ti(Of-Pr)4 (Scheme 4). In this reaction an allyl titanate, prodneed from an allylic alcohol and Ti(Oi-Pr)4, reacts with Pd(0) species to form a 7r-allylpalladium complex. The titanium alkoxide is replaced by the ligand exchange with the chloride ion to give a 7r-allyl palladinm complex, which undergoes facile carbonylation. Allylic methyl ethers can be carbonylated under severe conditions to give esters. ... 

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