Substituted aziridines by lithiation-electrophile trapping of terminal aziridines.

[reaction: see text] Regio- and stereoselective deprotonation of N-Bus (Bus = tert-butylsulfonyl)-protected terminal aziridines with lithium 2,2,6,6-tetramethylpiperidide generates a nonstabilized (H-substituted) aziridinyl anion that undergoes in situ or external electrophile trapping under experimentally straightforward conditions to give trans-disubstituted aziridines in good to excellent yields.

[1]  P. Dauban,et al.  Application of the Evans aziridination procedure to 2-substituted acrylates and cinnamates: An expedient route to α-substituted α- and β-amino acids , 1998 .

[2]  A. Mccamley,et al.  Synthesis and crystal structures of 2-substituted-2-phenylsulfonyloxiranes: evidence for a generalised anomeric effect in 2-phenylsulfonyloxiranes. , 2003, Organic & biomolecular chemistry.

[3]  K. Sharpless,et al.  Bromine-Catalyzed Aziridination of Olefins. A Rare Example of Atom-Transfer Redox Catalysis by a Main Group Element , 1998 .

[4]  D. Tanner Chiral Aziridines—Their Synthesis and Use in Stereoselective Transformations , 1994 .

[5]  Shengde Wu,et al.  Intramolecular Cyclizations of .alpha.-Lithioamine Synthetic Equivalents: Convenient Syntheses of 3-, 5-, and 6-Membered-Ring Heterocyclic Nitrogen Compounds and Elaborations of 3-Membered Ring Systems , 1994 .

[6]  Y. Fukuda,et al.  A new synthesis of enantiomerically pure α- and β-amino acid derivatives using aziridinyl anions , 2003 .

[7]  L. Frye,et al.  Sulfonylation of organometallic reagents with arenesulfonyl fluorides: a simple one-step synthesis of sulfones , 1992 .

[8]  J. Witherington,et al.  Unsaturated 1,2-amino alcohols and ethers from aziridines and organolithiums. , 2004, Chemical communications.

[9]  F. A. Davis,et al.  Recent Synthetic Applications of Chiral Aziridines , 2000 .

[10]  E. Jacobsen,et al.  General catalytic synthesis of highly enantiomerically enriched terminal aziridines from racemic epoxides. , 2004, Angewandte Chemie.

[11]  W. O. Moss,et al.  Lithiated aziridine reagents , 1993 .

[12]  P. Müller,et al.  Enantioselective catalytic aziridinations and asymmetric nitrene insertions into CH bonds. , 2003, Chemical reviews.

[13]  J. C. Martin,et al.  In situ trapping of ortho lithiated benzenes containing electrophilic directing groups , 1983 .

[14]  Armando Carlone,et al.  Asymmetric catalytic synthesis of enantiopure N-protected 1,2-amino alcohols. , 2004, Organic letters.

[15]  D. M. Hodgson,et al.  Substituted epoxides by lithiation of terminal epoxides. , 2004, Organic letters.

[16]  R. Fieldhouse,et al.  A novel procedure for the synthesis of aziridines: application of Simmons–Smith reagents to aziridination , 2001 .

[17]  T. Satoh Oxiranyl Anions and Aziridinyl Anions. , 1996, Chemical reviews.

[18]  M. Ferrara,et al.  Highly diastereoselective aziridination of imines with trimethylsilyldiazomethane. Subsequent silyl substitution with electrophiles, ring opening, and metalation of C-silylaziridines--a cornucopia of highly selective transformations. , 2002, The Journal of organic chemistry.

[19]  Pu Sun,et al.  tert-Butylsulfonyl (Bus), a New Protecting Group for Amines. , 1997, Journal of Organic Chemistry.

[20]  D. M. Hodgson,et al.  Straightforward synthesis of α,β-epoxysilanes from terminal epoxides by lithium 2,2,6,6-tetramethylpiperidide-mediated deprotonation-in situ silylation , 2002 .

[21]  A V Gontcharov,et al.  Tert-butylsulfonamide. A new nitrogen source for catalytic aminohydroxylation and aziridination of olefins. , 1999, Organic letters.

[22]  J. C. Martin,et al.  Direct, regiospecific 2-lithiation of pyridines and pyridine 1-oxides with in situ electrophilic trapping , 1983 .

[23]  M. Ashwell,et al.  Phenylsulphonyloxiranes as functionalised acyl anion equivalents in organic synthesis , 1991 .

[24]  Ferrara,et al.  Highly selective aziridination of imines using trimethylsilyldiazomethane and applications of C-silylaziridines in synthesis , 2000, Organic letters.

[25]  E. Vedejs,et al.  The stereochemistry of aziridine borane lithiation: diastereoselectivity and enantioselectivity , 2003 .

[26]  K. Oshima,et al.  Organoaluminum reagents of type R1R2NAlEt2 which allow regiospecific isomerization of epoxides to allylic alcohols , 1974 .

[27]  E. Vedejs,et al.  Aziridine Lithiation Using Lewis Acid Activation , 1997 .

[28]  J. Sweeney Aziridines: epoxides' ugly cousins? , 2002, Chemical Society reviews.

[29]  M. Apparu,et al.  Reactivite des epoxydes—III: Methodes de synthese d'hydroxyalkyl-1 vinyl-2 cyclopropanes: reactions d'epoxydes γ,δ-ethyleniques avec les amidures de lithium dans l'HMTP , 1978 .