Allylic compounds amines

In addition to the preparation of l-alkenes, the hydrogenolysis of allylic compounds with formate is used for the protection and deprotection of carboxylic acids, alcohols, and amines as allyl derivatives (see Section 2.9). 

N-Methyl-N,0-bis(trimethylsilyl)-hydroxylamine, 187 Amines (see also Allylic compounds,... 

Bismaleimides are produced by the condensation reaction of a diamine, such as methylenedianiline, with maleic anhydride. The reaction product tends to be crystalline with a high melting point. Eutectic blends of different bismaleimides reduce the melting point. However, a coreactant generally is required to improve the processing properties of the material. Bismaleimides owe their reactivity to the double bonds on each end of the molecule, which can react with themselves or with other compounds containing functional groups (vinyls, allyls. or amines). A typical bismaleimide structure is shown by ... 

Allyl compounds, 33 Allylic hydroperoxides, 34 Allyl trifluoromethanesulfonates, 35 Amination incidents, 35 Amine oxides, 35... 

Allylic phosphates are more reactive than allylic acetates. Chemoselective reaction of the allylic phosphate moiety of the bis-allylic compound 88 with one equivalent of malonate, without attacking the allylic acetate moiety, takes place to give 89. Then the aminated product 90 was obtained by the addition of amine [52],... 

Based on facile formation of 7i-allylpalladium intermediates from various allylic compounds, allyl groups can be used for the protection of carboxylic acids, amines and alcohols. Deprotection can be achieved by two methods using Pd(0) catalysts [128,138]. In one method, the allyl group can be removed as propylene by Pd-... 

The Tsuji-Trost Reaction (or Trost Allylation) is the palladium-catalyzed allylation of nucleophiles such as active methylenes, enolates, amines and phenols with allylic compounds such as allyl acetates and allyl bromides. 

The present chapter on modem allylic amination methods will be restricted mainly to an overview of some of the major developments for the transformation of allylic compounds into allyl amines according to reaction types (a) and (b) in Scheme 1, and an attempt is made to cover the literature up to August 1999. 

Dangerous fire and explosion hazard when exposed to heat, flame, or oxidizers. Highly reactive. When heated to decomposition it emits toxic fumes of NO. To fight fire, use alcohol foam, CO2, dry chemical. See also ALLYL COMPOUNDS and AMINES. 

SAFETY PROFILE Poison by ingestion, skin contact, and intraperitoneal routes. Moderately toxic by inhalation. Human systemic effects by inhalation route eye lachrymation and changes in the trachea or bronchi. A skin and severe eye irritant. A dangerous fire hazard when exposed to heat or flame. When heated to decomposition it emits toxic fumes of NOx. See also AMINES and ALLYL COMPOUNDS. 

A third alternative may also be conceived, if for a moment one disregards all the nonparticipant atoms in compound IV. What is left is just an allyl-vinyl amine, a molecular combination reminiscent of what is necessary to perform a Claisen-type rearrangement (see Problem 19). Application of this rationale to intermediate IV would lead to cis structure III in a smooth, concerted fashion. This transformation is known in the literature as the amino-Claisen rearrange-... 

It is well known that silylation of allyl derivatives with vinylsilane catalyzed by a ruthenium hydride complex is accompanied by isomerization ofpropen-l-yl to propen-2-yl derivatives as well as homo-coupling of vinylsilane when equimolar amounts of the initial substances are used. If catalyst I was used in the SC of allyl amide and allyl amine with vinylsilanes, a S-fold excess of olefin to vinylsilane was used to stop homocoupling of vinylsilane, but simultaneously no more than 5% of isomerization of allyl compound was observed [19, 26]. When allyl boronate is used instead of allylamine under mild conditions (20 - 40 °C), the two reactions catalyzed by I and IV yield stereoselectively -product (see Scheme 4) [26]. 

Nickel catalysts also catalyze Grignard substitution to allylic compounds including allyl alcohol [230-233] ethers [230,231,234,235 Eq. (106) 231] amines, albeit in a low product yield [231] sulfides [231,236,237], including thioacetals [238] thiols [231] selenides [239] carboxylates [240] phosphates [94,121] and halides [Eq. (107) 230], most likely via intermediate / -allyl-Ni species. Monosubstitution of bis-allyl ether was possible [Eq. (108) 235]. Most of the literatures cited in the foregoing disclosed regiochemical outcome associated with these allylic substitutions. 

Secondary amines are especially good nucleophiles for allylic substitutions. Alkylation-amination of the (Z)-bis-allylic compound shown below in the presence of Pd(PPh3)4 with one equivalent of malonate furnishes the bis-substitution product with ( )-selectivity. Alkene isomerization due to syn-anti interconversion in the 7t-allyl intermediate is often observed. 

Khazaei, A., Vaghei, R. G., Karkhanei, E. Bromination of organic allylic compounds by using N,N -dibromo-N,N -1,2-ethane diyi bis(2,5-dimethyl benzene sulfonyl)amine. Synth. Common. 2002, 32, 2107-2113. 

Allyl sulfides and allyl amines. Rhodium-catalyzed decomposition of ethyl diazoacetate in the presence of these allyl compounds generates products 136 and 137, respectively, derived from [2,3] rearrangement of an S- or N-ylide intermediate, besides small amounts of carbene dimers No cyclopropane and no product resulting from the ylide by [1,2] rearrangement were detected. Besides RhjfOAc) and Rhg(CO)i6, the rhodium(I) catalysts [(cod)RhCl]2 and [(CO)2RhCl]2 were found to behave similarly, but yields with the only allyl amine tested, CH =CH—CH NMe, were distinctly lower with the latter two catalysts. Reaction temperatures are higher than usually needed in rhodium-promoted diazoalkane decomposition, which is certainly due to competition between the diazo compound and the allylic hetero-... 

It has been noted that those morphine derivatives in which the nitrogen is allylic (compounds) can be degraded to dihydromethines by reduction of their methiodides with sodium in liquid ammonia (397), and the important observation has been made that a useful alternative to the Hofmann degradation consists in the decomposition of tertiary amine oxides, especially in those cases in which the Hofmann elimination results in loss of the side chain. It will also be noted that double bonds are not isomerized in this process (398) ... 

Two Pd-catalyzed cyclizations were used for the enantioselective synthesis of (—)-cephalotoxine [109]. One-pot Pd-catalyzed domino reactions, namely intramolecular allylation of amine and HR of 256, seem to be the best path for the desired synthesis. However, attempted direct conversion of 256 to 258 with the Herrmaim complex was unsuccessful. Then selective intramolecular aminoallylation with the chiral cyclopentyl acetate occurred smoothly to give the Spiro amine 257 in 88 % yield when Pd(PPh3)4 and TMG (tetramethylguanidine) as a base were used. The cyclization proceeded with retention of stereochemistry without racemization. The next HR reaction of 257 gave the seven-membered compound 258 in 81% yield under Jeffery s conditions using the Herrmann complex as a catalyst. No transformation of 257 to 258 occurred when Pd(PPh3)4 was used. The results show that the best catalysts for the allylation and HR are different. 

The Pd-catalysed allylation of carbon nucleophiles with allylic compounds via Jt-aUylpaUadium complexes is called the Tsuji-Trost reaction [32]. Typically, an allyl acetate or carbonate (54) reacts with a Pd-catalyst resulting in displacement of the leaving group to generate a Jt-allylpalladium complex (55) that can undergo substitution by a nucleophile (56) (Scheme 4.14). In 1965, Tsuji reported the reaction of ti-aUylpaUadium chloride with nucleophiles such as enamines and anions of diethyl malonate and ethyl acetoacetate. A catalytic variant was soon reported thereafter in the synthesis of allylic amines [33]. In 1973, Trost described the alkylation of alkyl-substituted 7i-aUylpalladium complexes with methyl methylsulfonylacetate... 

Hydrogenolysis of allylic compounds was rather general, including halides, acetates, alcohols, ethers and amines. 

Their reactivities are different. Although allylation with allylic chlorides proceeds without a Pd catalyst, their reaction is accelerated in the presence of a Pd catalyst. Allylic alcohols are rather poor substrates. Instead, their esters, typically allylic acetates, are used for smooth allylation. Allylic phosphates are more reactive than allylic acetates, and the chemoselective reaction of the allylic phosphate moiety of the bis-allylic compound with 1 equiv of malonate without attacking the allylic acetate moiety occurs (Scheme 5). Then the aminated product is obtained by the addition of amine. In addition to allylic esters, even allylic nitro compounds i-Piand sulfonest Hio] aHyiatjoj, Reactions of... 

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