Synthesis reaction with allylic halides

Acemoglu L, Williams JMJ (2002) Synthetic Scope of the Tsuji-Trost Reaction with Allylic Halides, Carboxylates, Ethers, and Related Oxygen Nucleophiles as Starting Compounds. In Negishi E, de Meijere A (eds) Handbook of Organopalladium Chemistry for Organic Synthesis. Wiley, New York, p 1689... 

Lespiau s [23] synthesis (in the same period) of 3-buten-l-ol (in 30% yield) by a Barbier reaction with allyl bromide, magnesium and trioxane - one of the earliest reports of Barbier reactions with allylic halides - has been mentioned in Sect. 2.3 (p. 20)... 

The cyclized analog of meralluride is prepared by a similar synthesis. Thus, condensation of camphoric acid (42) (obtained by oxidation of camphor) with ammonia gives the bicyclic succinimide (44). Reaction with allyl isocyanate followed by ring opening and then reaction with mercuric acetate affords the mercury derivative (45) as the acetate rather than the hydroxide as above. Reaction with sodium chloride converts that acetate to the halide (46). Displacement on mercury with the disodium salt of thioglycollic acid affords the diuretic mercaptomerine (47). ... 

Allylation of acyloyl-imidazoles and pyrazoles61 with allyl halide mediated by indium in aqueous media provides a facile regioselective synthesis of P, y-unsaturated ketones (Scheme 11.1), which has been applied to the synthesis of the monoterpene artemesia ketone. The same product can be obtained by indium-mediated allylation of acyl cyanide (Eq. 11.35).62 Samarium, gallium, and bismuth can be used as a mediator for the allylation of nitrones and hydrazones to give homoallylic hydroxylamine and hydrazides in aqueous media in the presence of Bu4NBr (Scheme 11.2).63 The reaction with gallium and bismuth can be increased dramatically under microwave activation. 

Monoanions derived from nitroalkanes are more prone to alkylate on oxygen rather than on carbon in reactions with alkyl halides, as discussed in Section 5.1. Methods to circumvent O-alkylation of nitro compounds are presented in Sections 5.1 and 5.4, in which alkylation of the a.a-dianions of primary nitro compounds and radial reactions are described. Palladium-catalyzed alkylation of nitro compounds offers another useful method for C-alkylation of nitro compounds. Tsuj i and Trost have developed the carbon-carbon bond forming reactions using 7t-allyl Pd complexes. Various nucleophiles such as the anions derived from diethyl malonate or ethyl acetoacetate are employed for this transformation, as shown in Scheme 5.7. This process is now one of the most important tools for synthesis of complex compounds.6811-1 Nitro compounds can participate in palladium-catalyzed alkylation, both as alkylating agents (see Section 7.1.2) and nucleophiles. This section summarizes the C-alkylation of nitro compounds using transition metals. 

Alkenyl-aluminum and -zirconium derivatives have been found to couple with allyl halides in the presence of Pd° catalysts (equation 38), although simple alkyl-aluminum and -zirconium reagents fail in the reaction.154 The 1,4-dienes thus generated are important intermediates in organic synthesis. 

Negishi, E.-I. Rand, C. L. Jadhav, K. P. Highly selective and convenient method for the synthesis of 1,5-enynes and 1,5-dienes by the reaction of 1,3-dilifhiopropargyl phenyl sulfide with allylic halides. J. Org. Chem. 1981, 46, 5041-5044. 

Stannylquinones.1 The quinone synthesis based on addition of alkynyllithiums to substituted cyclobutenediones (13, 209-210, 284) can provide stannylquinones. Thus thermolysis of the alkynylcyclobutenol 1 with Bu3SnOCH3 results in rearrangement to the stannylquinone 2. As expected, these stannylquinones undergo palladium-catalyzed cross-coupling with organic halides (Stille reaction, 14, 35), particularly with allylic halides. 

The second approach for the nucleophilic animation reactions to be considered here will be reactions of allyl halides and allyl acetates leading to allyl amines. Allyl halides are normally very reactive in SN2 reactions, but the direct coupling of allyl halides with nitrogen nucleophiles has been performed with limited success [4], as di- and trialkylated by products often predominate. The application of the Gabriel synthesis can to a certain extent eliminate the problem with polyalkylation of amines using, e.g., the stabilized phthalimide anion 19 as the nucleophile. The allyl amine 20... 

The reaction of allyl halides with organocopper species usually gives regiochemical mixture of direct and S 2 attack. Exceptions to this trend are 3,3-disubstituted 1-bro-moalkenes, which give reliable direct substitution with lower-order cuprates or RCu organocopper reagents. This fact has been put to use in the synthesis of several prenelated... 

Coupling reactions between allylic halides and alkynylcoppers have been rather heavily investigated as routes to stereochemically defined polyenyl natural products. The CuCl-catalyzed reaction of acetylenic Grignard reagents with chlorine substituted allylic chlorides has been employed in the synthesis of stereochemically pure 1,3,5-undecatrienes... 

Much of the recent interest in the arylstannanes, particularly the aryltrialkylstannanes, however, derives from their use in the Stille reaction in which an aryl-C bond is generated by reaction with a halide or sulfonate RX, where R = vinyl, allyl, benzyl, or aryl, to give Ar-R under catalysis by palladium68 or another transition metal.69-72 The reactions are very tolerant of various functional groups, and are finding wide application in organic synthesis, and are considered in Section 22.2. 

The synthesis of 1,5-dienes via the reaction of allyl halides and nickel carbonyl is now an indispensable process in synthetic organic chemistry. To our knowledge, it originates from the observation by Webb and Borcherdt (1951) that the reaction of l-chloro-2-butene or 3-chloro-l-butene with nickel carbonyl produced the dimeric 1,5-dienes in high yield. Later Corey and his... 

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