Scope and limitations in sulfur ylide mediated catalytic asymmetric aziridination of imines: use of phenyldiazomethane, diazoesters and diazoacetamides

VK Aggarwal*, Marco Ferrara, Christopher J O'Brien, Alison Thompson, Ray VH Jones, Robin Fieldhouse

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

99 Citations (Scopus)

Abstract

Imine aziridination using diazo-compounds and catalytic quantities of metal salts and sulfides has been investigated. A range of imines derived from benzaldehyde bearing electron-withdrawing groups (N-Ts, N-SO2CH2CH2SiMe3 (SES), N-P(O)Ph-2, N-CO2Bn, N-CO2But, N-CO2(CH2)(2)SiMe3, N-CO2C(CH3)(2)CCl3) were prepared and tested in the aziridination process using Me2S and phenyldiazomethane. High yields were obtained with all imines but diastereoselectivity varied considerably (3 : 1--> 10 : 1). A range of N-SES imines were tested with stoichiometric amounts of sulfides and high yields were obtained with both aromatic and aliphatic imines. These imines were subsequently testedwith stoichiometric and sub-stoichiometric loadings of enantiomerically pure 1,3-oxathiane 3 with Rh-2(OAc)(4) and with Cu(acac)(2). Good yields and high enantioselectivities (89-95%) were observed with Rh-2(OAc)(4), although a small reduction in enantiomeric excess was observed with Cu(acac)(2) (85-95%) especially when sub-stoichiometric amounts of sulfide were employed. The same sulfide was also tested with a range of electron-withdrawing groups on the imine nitrogen and in all cases good yields and high enantioselectivities were maintained. Improved diastereoselectivity was observed with carbamate groups.

The aziridination process was extended to include diazoester and diazoacetamides with a range of N-Ts imines, and again good yields were obtained although diastereoselectivity varied according to the diazo-compound employed. Although the 1,3-oxathiane 3 could not be employed with these more stable diazo-compounds, (R,R)-2,5-dimethylthiolane 5 was found to be a suitable chiral catalyst and gave moderate enantio- and diastereoselectivities. Rationales for the origin of the diastereoselectivity and enantioselectivity are provided.

Original languageEnglish
Pages (from-to)1635-1643
Number of pages9
JournalPerkin 1
Issue number14
DOIs
Publication statusPublished - 2001

Keywords

  • AZA-DARZENS REACTION
  • ENANTIOSELECTIVE AZIRIDINATION
  • CHIRAL AZIRIDINES
  • OLEFINS
  • ALDEHYDES
  • EPOXIDATION
  • DERIVATIVES
  • SULFINIMINES
  • MECHANISM
  • SULFIDES

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