Nucleophilic with nitrogen nucleophiles

Asymmetric allylation of carbon nucleophiles has been carried out extensively using Pd catalysts coordinated by various chiral phosphine ligands and even with nitrogen ligands, and ee > 90% has been achieved in several cases. However, in most cases, a high ee has been achieved only with the l,3-diaryl-substitiitcd allylic compounds 217, and the synthetic usefulness of the reaction is limited. Therefore, only references are cited[24,133]. 

Aluminum chloride [7446-70-0] is a useful catalyst in the reaction of aromatic amines with ethyleneknine (76). SoHd catalysts promote the reaction of ethyleneknine with ammonia in the gas phase to give ethylenediamine (77). Not only ammonia and amines, but also hydrazine [302-01-2] (78), hydrazoic acid [7782-79-8] (79—82), alkyl azidoformates (83), and acid amides, eg, sulfonamides (84) or 2,4-dioxopyrimidines (85), have been used as ring-opening reagents for ethyleneknine with nitrogen being the nucleophilic center (1). The 2-oxopiperazine skeleton has been synthesized from a-amino acid esters and ethyleneknine (86—89). 

The polymerization of ethyleneimine (16,354—357) is started by a catalyticaHy active reagent (H or a Lewis acid), which converts the ethyleneimine into a highly electrophilic initiator molecule. The initiator then reacts with nitrogen nucleophiles, such as the ethyleneimine monomer and the subsequendy formed oligomers, to produce a branched polymer, which contains primary, secondary, and tertiary nitrogen atoms in random ratios. Termination takes place by intramolecular macrocycle formation. 

Reaction at position 4 of perfluotopyndme thus occurs readily with nitrogen nucleophiles, as exemplified by its reactions with sodium azide and with hydroxyl-amme [75, 76] (equation 39)... 

Phosphorus nucleophiles have received little attention compared with nitrogen nucleophiles in reactions with fluonnated systems Yields with phosphorus nucleophiles are sometimes low, but interesting materials are obtained [80, 81] (equations 42 and 43). 

This trend is also observed in the reactions with nitrogen- and carbon-centered nucleophiles (2001H425). Thus, the reaction of 109 with sodium indolyl in DMF affords methyl 2-(indol-l-yl)indole-3-carboxylate (188, 77%). In better yield, 2-(indol-l-yl)indole-3-carbaldehyde (189, 95%) is formed in the corresponding reaction (99H1157) of 115a (Scheme 28). Sodium imidazolyl reacts with 109 in DMF at 60°C to afford methyl 2-(imidazol-l-yl)indole-3-carboxylate (190,28%), methyl indole-3-carboxylate (191,11 %), and unreacted 109 (36%). In contrast, under the same conditions, 110 and 115a provide higher yields of methyl 2-(imidazol-... 

With Nitrogen Nucleophiles Aziridine-2-carboxylates react with primary and secondary amines, including anilines, to give a, 3-bisamino carboxylates [71, 113]. As an example, treatment of aziridine 153 (Scheme 3.55) with diethylamine in methylene chloride afforded compound 154 in 89% yield after chromatographic separation. 

Reaction of 3-benzamido-2,5-dioxo-5,6,7,8-tetrahydro-(2ff)-l-benzopyrans 58 with nitrogen-containing nucleophiles (amines and hydrazines) provides the corresponding quinolin-2-(l//)-ones 59 <96H(43)809>. 

The l-imino-lff-2-benzopyran (13) ring opens on treatment with nitrogen nucleophiles. Different modes of recyclisation are possible and (13) is therefore a source of a variety of -heterocycles <96AJC485>. 

B. Reactions.—(/) Nucleophilic Attack at Phosphorus. A reinvestigation of the reaction between phosphorus trichloride and t-butylbenzene in the presence of aluminium chloride has shown that the product after hydrolysis is the substituted phosphinic acid (11), and not the expected phosphonic acid (12). Bis(A-alkylamino)phosphines have been reported to attack chlorodiphenyl phosphine with nitrogen, in the presence of a base, to give bis-(A-alkyl-A-diphenylphosphinoamino)phenylphosphines (13). In (13), the terminal phosphorus atoms are more reactive than the central one towards sulphur and towards alkyl halides. 

B. Palladium-catalyzed substitution with nitrogen nucleophiles 4d... 

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