Blum–Ittah aziridine synthesis

The Blum–Ittah aziridine synthesis, also known as the Blum–Ittah-Shahak aziridine synthesis[1] or simply the Blum aziridine synthesis is a name reaction of organic chemistry, for the generation of aziridines from oxiranes.[2][3][4][5][6][7][8][9]

Blum–Ittah aziridine synthesis
Named after Jochanan Blum
Ytzhak Ittah
Reaction type Ring forming reaction

Mechanism

The oxirane is first converted into a 2-azidoalcohol with the use of an azide such as sodium azide. The azido alcohol is then reduced with the use of a trialkylphosphine such as triphenylphosphine in a manner similar to the Staudinger reaction, concomitant with loss of N2. The resulting phosphonimine (formerly called iminophosphorane) intermediate is then attacked by the alcohol, with oxygen forming a bond with the phosphorus atom. Forming a ring intermediate. After a proton transfer, a pair of electrons from the oxygen atom shifts onto the phosphorus atom, and the phosphorus-nitrogen bond breaks, with the electron pair shifting onto the nitrogen atom. The negatively charged nitrogen atom attacks the carbon atom that the oxygen atom is connected to. This gives us our desired aziridine and a trialkylphosphine oxide as a side product.[2][3][4][7][9]

Applications

The Blum-Ittah aziridine synthesis has been used in the synthesis of α-methylserine[5] and 6-Azabicyclo[3.2.1]octanes.[8]

References
  1. Hassner, Alfred; Namboothiri, Irishi (5 January 2012). Organic Syntheses Based on Name Reactions: A Practical Guide to 750 Transformations. Elsevier. p. 51. ISBN 978-0-08-096630-4.
  2. Ittah, Ytzhak; Sasson, Yoel; Shahak, Israel; Tsaroom, Shalom; Blum, Jochanan (1978-10-01). "A new aziridine synthesis from 2-azido alcohols and tertiary phosphines. Preparation of phenanthrene 9,10-imine". The Journal of Organic Chemistry. 43 (22): 4271–4273. doi:10.1021/jo00416a003.
  3. Ittah, Ytzhak; Shakah, Israel; Blum, Jochanan (1978-02-01). "Stable arene imines". The Journal of Organic Chemistry. 43 (3): 397–402. doi:10.1021/jo00397a004.
  4. Tanner, David; He, Hua Ming; Somfaib, Peter (1992-05-18). "Regioselective nucleophilic ring opening of 2,3-aziridino alcohols". Tetrahedron. 48 (29): 6069–6078. doi:10.1016/S0040-4020(01)89855-0.
  5. Wipf, Peter; Venkatraman, Srikanth; Miller, Chris P. (1995-05-22). "A new synthesis of α-methylserine by nucleophilic ring-opening of N-sulfonyl aziridines". Tetrahedron Letters. 36 (21): 3639–3642. doi:10.1016/0040-4039(95)00621-I.
  6. Fürmeier, Sandra; Metzger, Jürgen O. (2003-01-23). "Fat-Derived Aziridines and Their N-Substituted Derivatives: Biologically Active Compounds Based on Renewable Raw Materials". European Journal of Organic Chemistry. 2003 (4): 649–659. doi:10.1002/ejoc.200390105.
  7. Hili, Ryan; Yudin, Andrei K. (2006-10-27). "Readily Available Unprotected Amino Aldehydes". Journal of the American Chemical Society. 128 (46): 14772–14773. doi:10.1021/ja065898s. PMID 17105264.
  8. Pulipaka, Aravinda B.; Bergmeier, Stephen C. (2008-01-23). "A Synthesis of 6-Azabicyclo[3.2.1]octanes. The Role of N-Substitution". The Journal of Organic Chemistry. 73 (4): 1462–1467. doi:10.1021/jo702444c. PMID 18211092.
  9. Li, Jie Jack (2006). Name Reactions A Collection of Detailed Reaction Mechanisms. Springer. p. 63. ISBN 978-3-540-30030-4.


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