Aldimines compounds

Metal derivatives of ketimine and aldimine compounds. D. F. Martin, Prep. Inorg. React., 1964,1, 59-75 (48). 

Aldimine Compound of the general type RCH=NR. Also called an azomethine. 

If, however, hydrogen is present in the a-position of the iV-alkyl substituent, 2-alkyl-oxaziridines are easily decomposed by alkali. Base attack on this H atom effects 1,2-elimination at the C—N bond. From (86) and aldimine (87) forms, and a mixture of ammonia and two carbonyl compounds is finally obtained, one of them containing the carbon atom of the original oxaziridine ring, the other originating from the IV-alkyl group (57JA5739). 

Halogen-free A/-acyl aldimines and N-acyl ketiimnes tautomenze readily to give enamides [J6] In contrast, perfluonnatedyV-acylimines are stable compounds These electron-deficient itnmes not only exhibit high thermal stability but also show umque properties both as electrophiles and as strongly polanzed hetero-1,3-dienes... 

The reaction of crotyl organometallic compounds 1 with aldimines 2 results in linear 3 or branched 4 homoallylamines. 

Isocyanides that do not contain an a hydrogen react with alkyllithium compounds, as well as with Grignard reagents, to give lithium (or magnesium) aldimines. These metalated aldimines are versatile nucleophiles and react with various substrates as follows ... 

In all the above reactions, secondary amines give good yields of butenyl compounds, whereas with primary amines products of high molecular weight, i.e. containing more than 2 butadiene units per mol of amine, are also formed. The latter have been shown to be aldimine derivatives containing three C4 units [203]. 

In general, an aldimine is among the least reactive carbonyl compounds and is by far less reactive than an aldehyde [31-33]. Nevertheless, the Et2Zn-Ni catalytic system is successfully extended to the homoallylation of aldimine. Aldimine prepared in situ from an aldehyde and a primary aromatic amine undergoes the homoallylation smoothly under the essentially identical con-... 

The formimidoyl group can be transferred onto either amines, alcohols or CH-active compounds without use of a catalyst, providing amidines or aldimines and enamines, respectively [31... 

Dichloroneopentylsilene is formed in situ by reaction of trichlorovinylsilane with LirBu [1], The [2+2] cycloaddition to imines yields Si-dichloro functionalized 2-silaazetidines in a preparative scale [2], When aldimines are used as trapping agents for the silene, the resulting SiN-four membered ring compounds are isolated as syn/anti-isomers (syn/anti 2/1). 

Aziridines have been synthesized, albeit in low yield, by copper-catalyzed decomposition of ethyl diazoacetate in the presence of an inline 260). It seems that such a carbenoid cyclopropanation reaction has not been realized with other diazo compounds. The recently described preparation of 1,2,3-trisubstituted aziridines by reaction of phenyldiazomethane with N-alkyl aldimines or ketimines in the presence of zinc iodide 261 > most certainly does not proceed through carbenoid intermediates rather, the metal salt serves to activate the imine to nucleophilic attack from the diazo carbon. Replacement of Znl2 by one of the traditional copper catalysts resulted in formation of imidazoline derivatives via an intermediate azomethine ylide261). 

Aldimines, Ketimines, and Related Compounds as Dipolarophiles Reactions of aldimines with nitrile oxides proceed readily to give 1,2,4-oxadiazolines independently of the nature of substituents both in dipole and dipolarophile molecules. 1,2,4-Oxadiazolines were prepared by the regiospe-cihc 1,3-dipolar cycloaddition of nitrile oxides with fluoro-substituted aldimines (295). Phosphorylnitrile oxides gave with azomethines, PhCH NR, phosphory-lated 1,2,4-oxadiazolines 129 (296). Expected 1,2,4-oxadiazolines were also obtained from azomethines, derived from 4-formylcoumarine (179) and 1,3-diphenylpyrazole-4-carbaldehyde (297). 

Intramolecular process with rhodium catalyst has been described for the syntheses of indane, dihydroindoles, dihydrofurans, tetralins, and other polycyclic compounds. Wilkinson catalyst is efficient for the cyclization of aromatic ketimines and aldimines containing alkenyl groups tethered to the K z-position of the imine-directing group. 

Rhodium complexes catalyze 1,2-addition of main group metal compounds to aldimines as well. Table 5 summarizes the reported methods. Electron-withdrawing substituents such as sulfonyl and acyl groups on the imino nitrogen atom are important to obtain sufficiently high reactivity. Asymmetric synthesis (diastereoselective and enantioselective) has also been accomplished. 

Intramolecular addition of trialkylboranes to imines and related compounds have been reported and the main results are part of review articles [94, 95]. Addition of ethyl radicals generated from Et3B to aldimines affords the desired addition product in fair to good yield but low diaster control (Scheme 40, Eq. 40a) [96]. Similar reactions with aldoxime ethers [97], aldehyde hydrazones [97], and N-sulfonylaldimines [98] are reported. Radical addition to ketimines has been recently reported (Eq. 40b) [99]. Addition of triethylborane to 2H-azirine-3-carboxylate derivatives is reported [100]. Very recently, Somfai has extended this reaction to the addition of different alkyl radicals generated from trialkylboranes to a chiral ester of 2ff-azirine-3-carboxylate under Lewis acid activation with CuCl (Eq. 40c) [101]. 

Scheme 40 Addition of trialkylboranes to aldimines, ketimines and related compounds...

In the absence of substrates, the aldehyde group of pyridoxal phosphate is covalently bound to a lysine residue of the transaminase (1). This type of compound is known as an aldimine or Schiffs base. During the reaction, amino acid 1 (A, la) displaces the lysine residue, and a new aldimine is formed (2). The double bond is then shifted by isomerization. 

Leaving precise mechanistic arguments aside, it should be stressed that an a,/9-unsatu-rated carbonyl compound can behave as a latent nucleophile with the assistance of a hydrosilane and a low-valence rhodium complex. With this simplification, isocyanates 18 and aldimines 20 were used as electrophiles for a similar protocol. Both were successfully incorporated with the aid of [Rh(COD)(P(OPh)3)2]OTf to afford 19 and 21, respectively (Scheme 6.5) in a reaction that was similar to the aldol-type coupling [11]. 

---