De Kimpe aziridine synthesis

De Kimpe aziridine synthesis
Named after	Norbert De Kimpe
Reaction type	Ring forming reaction
Identifiers
Organic Chemistry Portal	de-kimpe-aziridine-synthesis

The De Kimpe azirdine synthesis is a name reaction of organic chemistry, for the generation of aziridines by the reaction of α-chloroimines with nucleophiles such as hydride,[1] cyanide, or Grignard reagents.[2][3]

The De Kimpe aziridine synthesis is suitable for both aldimines and ketimines, particularly those with two alkyl substituents on the α-carbon (Thorpe-Ingold effect).[4]

Mechanism

The nucleophile attacks the imino carbon atom, forming a tetrahedral intermediate. The intermediate then undergoes an intramolecular nucleophilic substitution, with the negatively charged nitrogen atom attacking the α-carbon and having the chloride anion as the leaving group.

References

De Kimpe, Norbert; Moens, Luc (6 February 1990). "Synthesis of 1,2,3-trisubstituted and 1,2,2,3-tetrasubstituted aziridines from α-chloroketimines". Tetrahedron. 46 (8): 2965–2974. doi:10.1016/S0040-4020(01)88388-5.
"Asymmetric Synthesis of Aziridines by Reduction of N-tert-Butanesulfinyl α-Chloro Imines". The Journal of Organic Chemistry. 72 (9): 3211–3217. 31 March 2007. doi:10.1021/jo0624795. PMID 17397222.
Denolf, Bram; Mangelinckx, Sven; Törnroos, Karl W.; Norbert, De Kimpe (14 June 2006). "Use of α-Chlorinated N-(tert-Butanesulfinyl)imines in the Synthesis of Chiral Aziridines". Organic Letters. 8 (14): 3129–3132. doi:10.1021/ol0611245. PMID 16805569.
de Kimpe, Norbert; Verhé, Roland; de Buyck, Laurent; Schamp, Niceas (1 January 1977). "Reaction of secondary N‐1‐(2‐chloroalkylidene)amines with lithium tetrahydridoaluminate: Synthesis and rearrangement of 1,2,2‐trisubstituted aziridines". Recueil des Travaux Chimiques des Pays-Bas. 96 (9): 242–246.

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[1] De Kimpe, Norbert; Moens, Luc (6 February 1990). "Synthesis of 1,2,3-trisubstituted and 1,2,2,3-tetrasubstituted aziridines from α-chloroketimines". Tetrahedron. 46 (8): 2965–2974. doi:10.1016/S0040-4020(01)88388-5.

[2] "Asymmetric Synthesis of Aziridines by Reduction of N-tert-Butanesulfinyl α-Chloro Imines". The Journal of Organic Chemistry. 72 (9): 3211–3217. 31 March 2007. doi:10.1021/jo0624795. PMID 17397222.

[3] Denolf, Bram; Mangelinckx, Sven; Törnroos, Karl W.; Norbert, De Kimpe (14 June 2006). "Use of α-Chlorinated N-(tert-Butanesulfinyl)imines in the Synthesis of Chiral Aziridines". Organic Letters. 8 (14): 3129–3132. doi:10.1021/ol0611245. PMID 16805569.

[4] Kimpe, Norbert; Verhé, Roland; de Buyck, Laurent; Schamp, Niceas (1 January 1977). "Reaction of secondary N‐1‐(2‐chloroalkylidene)amines with lithium tetrahydridoaluminate: Synthesis and rearrangement of 1,2,2‐trisubstituted aziridines". Recueil des Travaux Chimiques des Pays-Bas. 96 (9): 242–246.