Allylmagnesium chloride, reaction with

Finally, an example of solid support reaction quenching [133] is reported in Figure 7.18. Six aldehydes were reacted with allylmagnesium chloride or with -butyllithium to produce reactive alkoxides in solution. They were quenched by the carboxylic resin 4, which also scavenged the excess of the... 

Reaction of methyl quinolinylsulfoxide (86) with allylmagnesium chloride or with 1-methylallyl-magnesium chloride led to the 2-allyl and 2-(l-methylallyl)quinoline, (87) and (88) respectively, contaminated with unseparable isomeric a,p-unsaturated derivatives, in high yields. ... 

Allylmagnesium bromide, 41, 49 reaction with acrolein, 41, 49 5-Allyl-l,2,3,4,5-pentachlorocyclopen-tadiene, 43, 92 Allyltriphenyltin, 41, 31 reaction with phenyllithium, 41, 30 Aluminum chloride, as catalyst, for isomerization, 42, 9 for nuclear bromination and chlorination of aromatic aldehydes and ketones, 40, 9 as Friedel-Crafts catalyst, 41, 1 Amidation, of aniline with maleic anhydride, 41, 93... 

Glyoxal-sodium bisulfite, 30, 86 Glyoxylic acid, w-butyl ester, 35, 18 ethyl ester, diethyl acetal, 35, 59 Grignard reaction, addition to ethyl sec-butylidenecyanoacetate, 35, 7 allylmagnesium bromide with of,(3-di-bromoethyl ethyl ether, 36, 61 allylmagnesium chloride with a,/3-di-bromoethyl ethyl ether, 36, 63 ethylmagnesium bromide with tin tetrachloride, 36, 86... 

Reactions of Allylation and Propargylation Allylation of prochiral and chiral nitrones (292) with allylmagnesium chloride leads to homoallylic hydroxylamines (416), which via an iodo cyclization step are converted to 5-(iodomethyl)isoxazolidines (417) (Scheme 2.186) (202, 213, 666-668). 

Another method for the alkylidenation of aldonolactones uses addition of organ-ometallic reagents [78]. For example, Lin et al. [85] described an efficient route to conjugated anomeric dienes or aldehydes based on the reaction of aldono-1,4- and aldono-1,5-lactones (1, 62) with allylmagnesium chloride (Scheme 19), giving allyl hemiacetals (e.g., 63a, b). Hemiacetal can be dehydrated [e.g., with (CF3C0)20] to produce dienes 64a, b, or ozonolyzed (e.g., to give 65). 

The reaction of allylmagnesium chloride with methylaluminium dichloride affords, after workup of the reaction mixture and recrystalUzation from THF, a rather unexpected compound (7), which, according to its crystal-strucmre determination, appears to consist of [(allyl)2Mg3Cl3(THF)6]+ cations and [(allyl)4Mg] anions in a 2 1 molar ratio (Figure 8). ... 

A new synthesis of propenyl ketones involves reaction of an ester with 2 equiv. of allylmagnesium chloride (or methallylmagnesium chloride) to form the tertiary... 

Fig. 4.47) of up to the fourth generation with terminal chloride functions [90], These could be transformed into the corresponding terminal functional groups, for example by reaction with p-phenylphenol, p-bromophenol, lithium phenyl-acetylide, or allylmagnesium bromide. 

Similar to the formation of allylmagnesium chloride (25), the oxidative addition of allyl halides to transition metal complexes generates allylmetal complexes 26. However, in the latter case, a 7i-bond is formed by the donation of 7i-electrons of the double bond, and resonance of the n-allvl and 7i-allyl bonds in 26 generates the 7i-allyl complex 27 or (/ -allyl complex. The carbon-carbon bond in the 7i-allyl complexes has the same distance as that in benzene. Allyl Grignard reagent 25 is prepared by the reaction of allyl halide with Mg metal. However, the 7i-allyl complexes of transition metals are prepared by the oxidative addition of not only allylic halides, but also esters of allylic alcohols (carboxylates, carbonates, phosphates), allyl aryl ethers and allyl nitro compounds. Typically, the 7i-allylpalladium complex 28 is formed by the oxidative addition of allyl acetate to Pd(0) complex. 

Enantioselective ally lotion.1 The reaction of 2 with allylmagnesium chloride in ether affords a chiral orange allyltitanium complex 3. This complex reacts with an aldehyde at —78° to afford homoallyl alcohols in 55-88% yield and in 86-94% ee and with release of 1 and a titanate that can be reconverted to CpTiCl3 (equation I). Reaction of 3 with aryl ketones requires a temperature of 0°, and the enantioselectiv-ity is only about 50%. 

Treatment of enantiomerically pure cyclic sulfonimidates 6 and 7 with allyllithium or allylmagnesium bromide gives optically active allylic sulfoximines 8 and 9 (R = allyl) as described in Section II.A.13 The reactions of /V-phenyl-S-(methyl-phenyl)sulfoximidoyl chloride 109 with allyltrimethylsilane or allyltributylstan-... 

Even the reaction of allylmagnesium chloride with the imine shows moderate. vv -selec-tivity. 

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