Aminals s. a. 1,1-Diamines

Alkylideiie-bis-amines s. 1,1-Diamines a-Alkylidenecyclanones (s. a. a-Alkylidenecyclo-pentanones)... 

Primary and secondary amines also react with epoxides (or in situ produced episulfides )r aziridines)to /J-hydroxyamines (or /J-mercaptoamines or 1,2-diamines). The Michael type iddition of amines to activated C—C double bonds is also a useful synthetic reaction. Rnally unines react readily with. carbonyl compounds to form imines and enamines and with carbo-tylic acid chlorides or esters to give amides which can be reduced to amines with LiAlH (p. Ilf.). All these reactions are often applied in synthesis to produce polycyclic alkaloids with itrogen bridgeheads (J.W. Huffman, 1967) G. Stork, 1963 S.S. Klioze, 1975). 

With the chiral diamine (S,S)-20 as a co-catalyst full conversion was obtained in all cases, indicating that the amine has a pronounced influence on reactivity and selectivity (entries 9-14). The combination (R Rc)-4ael/(S,S)-20 afforded 18a as an almost racemic mixture (entry 9). The value of 6% ee (R) obtained in this experiment reflects two opposite contributions. On one hand, the system chiral phosphorous ligand/achiral diamine (R Rc)-4ael/19 led to 18a with 65% ee (S) (entry 1). On the other hand, an ee value of 75% (R) in the hydrogenation of 1-acetonaphthone has been reported for the system achiral phosphine (PPh3)/(S,S)-20 [41] This indicates that two inductions are canceled in an almost additive way in the mixed system. 

Alternatively, the remaining sulfate ester of 70 may serve as a leaving group for a second nucleophilic displacement reaction. When this displacement is by an intramolecular nucleophile, a new ring is formed, as was first shown in the synthesis of a cyclopropane with malonate as the nucleophile [68] and of aziridines with amines as the nucleophiles [76]. The concept is further illustrated in the double displacement on (/J,/ )-stilbenediol cyclic sulfate (72) by benzamidine (73) to produce the chiral imidazoline 74 [79]. Conversion of the imidazoline (74) to (.V,.S )-stilbenediaminc 75 demonstrates an alternative route to optically active 1,2-diamines. Acylation of 75 with chloroacetyl chloride forms a bisamide, which, after reduction with diborane, is cyclized to the enantiomerically pure trans-2,3-diphenyl- 1,4-diazabicy-clo[2.2.2]octane (76) [81],... 

A catalytic approach to the synthesis of arylglycines was proposed by Evans and coworkers using enantioselective amination of iV-acy 1 oxazolidinones [54], Metallo-bis(sulfonamide) complexes derived from chiral diamines are potential chiral catalysts. The magnesium-bis(sulfonamide) complex 109 was generated by treating (S,S)-bis(sulfonamide) 108 with dimethylmagnesium in dichloromethane (Scheme 50). 

Schiff bases commonly employ polyamines as reagents, the donor nature of the ligands depending both on the type of aldehyde or ketone used and the nature of primary amine or diamine. Scheme 1 illustrates some ways of obtaining Schiff bases of different denticities via 1 1 reactions of aldehydes with ketones to yield mixed N, O, S, and Se donor sets. Condensation of aldehydes and ketones with a-amino acids is also known. Where two moles of a carbonyl compounds and one mole of diamine are reacted, more elaborate Schiff bases with higher denticity result, also exemplified in Scheme 1. 

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