N-Allylanilines

Anilinotrimethylsilane 1599 (1.65 g, 10 mmol), NaOMe (0.54 g, 10 mmol), and allyl bromide (1.21 g, 10 mmol) are stirred in 25 mb abs. THF and 5 mb diglyme for 18 h at 40 °C. The mixture is quenched with water and extracted with hexane. The organic layer is washed several times with water, dried over MgS04, the solvent is evaporated, and the residue is chromatographed in benzene over a column of silica gel to afford 0.95 g (72%) pure N-allylaniline 1601 [11] (Scheme 10.23). 

Dialkylindolines and 1,3-dialkylindoles are formed in poor yield (<10%) from the reaction of ethyl- or phenymagnesium bromide with 2-chloro-N-methyl-N-allylaniline in the presence of catalytic quantities of (bistriphenylphosphine)nickel dichloride.72 In a modification of this procedure, the allyl derivatives can be converted by stoichiometric amounts of tetrakis(triphenylphosphine)nickel into 1,3-dialkylindoles in moderate yield72 (Scheme 43) an initial process of oxidative addition and ensuing cyclization of arylnickel intermediates is thought to occur. In contrast to the nickel system,72 it has proved possible to achieve the indole synthesis by means of catalytic quantities of palladium acetate.73 It is preferable to use... 

The application of Heck cyclizations to the synthesis of indoles, indolines, and oxindoles was discovered independently by Mori-Ban s [296-298], and Heck s groups [299]. These investigators found that Pd can effect the cyclization of o-halo-N-allylanilines to indoles under Heck conditions [300]. The cyclization of o-halo-N-allylanilines to indoles is a general and efficient methodology, especially with the Larock improvements where he cyclized o-halo-JV-allylanilines and o-halo-iV-acryloylanilides into indoles and oxindoles [301]. For example, the conversion of 279 to 280 can be performed at lower temperature, shorter reaction time, and with less catalyst to give 3-methylindole (280) in 97% yield. Larock s improved conditions, which have been widely adopted, are catalytic (2%) Pd(OAc)2, /1-BU4NCI, DMF, base (usually... 

N-Allylaniline Azide, C9Hi0N4 —not found in Beil or CA through 1956 N-Allylnitroaniline, C Hl0N,O mw 178.19,... 

Phenylallylamine. See N-Allylaniline A136-R Phenylallylozonide. See Allylbenzeneozonide A137-L... 

A series of reactions of nitroarenes with triallyl-, trimethallyl- and tricrotylborane have been studied. It has been established that the major process is reductive allylboration of nitro-groups accompanied by an allylic rearrangement. As a result, a new convenient method of the synthesis of N-allylanilines has been elaborated. 

CLAISEN-IRELAND Rearrangement Rearrangement of allyl phenyl ethers to o-(or p)-allylphenols or of allyl vinyl ethers to y,8-unsaturated aldehydes or ketones (Claisen). Rearrangement of allyl esters as enolate anions or silyl enol ethers to y,5-unsaturated acids (Ireland). Also rearrangement of N-allylanilines (an aza-Cope rearrangement) (see 1st edition). 

Diallyl (1) ( 30%) was distilled off and W-allylaniline (4) (45—60%), iV, -diallylaniline (5) (8—10%) and allylalcohol ( 5%) were isolated after deboronation of the residue (Table 1). Negligible amounts of aniline as well as the products of allylation of N-allylaniline in aromatic ring and in a-position of the allylic group were also detected. Trimethallylborane reacts in the same way to produce dimethallyl (33%), A -methallylaniline (57%), A, 7V-dimethallylaniline (8.5%) and negligible co-products. Similar products were isolated fi om the allylboration of / -chloronitrobenzene, and o- and p-nitrobiphenyl (Table 1). 

Heck indole synthesis, and Hegedus-Mori-Heckreaction, in general contains at least two types of reactions for indole derivatives. They are the palladium (n) complex-catalyzed oxidative A -heterocyclization of o-allylaniline (developed in 1976) or o-aminostyrenes (reported in 1978) and the palladium-catalyzed intramolecular cyclization of o-halo N-allylaniline (reported in 1980) the latter preparation is also referred to as the Hegedus cyclization. ... 

An ethereal soln. of phenyllithium added to startg. chlorallylamine in THF at —78° under argon, stirred for 30 min at the same temp., a soln. of Li-naphthalenide in the same solvent added, the mixture stirred for a further 2 h, water added, and allowed to warm to room temp, overnight - N-allylaniline. Y 93%. F. electrophiles, also syntheses via N-acylallylamine N,C-dianions, and prepn. of propargylamines from N-alkyl derivs., s. J. Barluenga et al., J. Chem. Soc. Perkin Trans. I 1989, 553-7. 

Treatment of N-allylanilines with mercury(ll) acetate leads to intermediate piperazines, which are readily transformed into the methyl-substituted derivatives/ The steric course of the reaction is strongly influenced by the steric demand of groups in either the allylic group or the ortho-position of the aryl ring of the amine (Scheme 89). 

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